Taryon is canonically gay, as revealed in "Jugs and Rods" (1x94). In the episode, Tary describes a past relationship with an old tutor named Lawrence, and in "The Chapter Closes" (1x115), Tary is revealed to have found Lawrence and "picked up where they left off".
Scanlan was shown to be attracted to both men and women throughout the campaign. In "The Ominous March" (1x109), Scanlan is tricked into drinking a love potion by Vax'ildan and Grog, after which he first sees Percy and falls in love with him for the duration of the effect. The player, Sam Riegel was asked by Dungeon Master Matthew Mercer how adventurous Scanlan had been in his various exploits, as the love philter only worked if the character already found the other person's gender and species attractive. Sam responded by saying "A human man? That was teenage years, baby. I've gone much further than that since then."
Vax'ildan is bisexual, as confirmed by Liam O'Brien in a Q&A.. Before cementing his relationship with Keyleth, Vax often flirted with Gilmore and kissed him after officially ending their courtship . Additionally, Vax stated multiple times his attraction to both men and women, once while masquerading as Scanlan in Vasselheim.
Vex'ahlia was shown to flirt with both men and women throughout the campaign, and as such is often referred to as bisexual. Laura Bailey said on Twitter that "Vex needs to find herself a man. Or a woman." in regards to discussion on shipping on Critical Role.
Zahra Hydris Edit
From the outset Zahra and Vex had a semi-antagonistic but very flirty and teasing relationship, and the two grew to be close friends. When asked about her relationship to Vex, Mary Elizabeth McGlynn said in a Q&A that Zahra feels attractiveness goes beyond the physical, that there was an "attraction to someone's soul".
Gilmore is gay, and has only shown attraction to men in game. He was involved in a flirtatious relationship with Vax'ildan, and when visiting his childhood home in "The Streets of Ank'Harel" (1x65), Vex'ahlia found letters from Gilmore to a male lover, as confirmed in the campaign wrap-up episode of Talks Machina.
J'mon Sa OrdEditJ'mon Sa Ord is an androgynous humanoid described as beautiful and looking both and neither male nor female. They use the gender-neutral pronouns “they/them”, however Matthew Mercer sometimes refers to them with “she/her” and “he/him” pronouns, suggesting that perhaps J’Mon is genderfluid.
Lady Kima of VordEdit
Lady Kima of Vord is shown to be attracted to women in canon, and is presumed to be a lesbian in reference to Grog’s vain attempts of romancing her. In "The Feast" (1x24), Allura implied Kima’s sexuality when Tiberius Stormwind suggested a double-date with them and Grog. Allura stated that Grog and Kima would not be a good match. Additionally, Kima eventually married Allura Vysoren as revealed in "Taryon, My Wayward Son" (1x97).
Allura is bisexual, as confirmed by Matthew Mercer in an episode of Talks Machina. She humored the flirtations of Tiberius Stormwind, but after Vox Machina's rescue mission in Kraghammer, Allura reconnected with Lady Kima of Vord. The two were later revealed to have married in "Taryon, My Wayward Son" (1x97).
The Mighty NeinEdit
Beau is a lesbian. In game, she has only shown attraction to women, and has been confirmed by Marisha Ray to be a lesbian in Talks Machina. She has been described by fans as a "disaster lesbian" to which Marisha responded that there are no better words to describe her. Beauregard has had three intimate encounters with women in game, two of which including guest player characters Keg and Reani  respectively.
Mollymauk is genderfluid and bisexual, as confirmed by Matthew Mercer in an interview on the DnD Beyond twitch channel.  As for visibility in game, in "Whispers of War" (2x18), Molly purchased a night with two companions, and when asked his preference for male or female, he responded with "surprise me". The two ended up being a male and a female.
Reani is bisexual. She was planning to marry an elven woman named Fen before their disagreements split them apart, and she showed her attraction to Essek Thelyss in game  and to Caleb, as confirmed by player Mica Burton on Talks Machina. Additionally, Reani gave a rose to and shared a kiss with Beauregard, afterwords spending unspecified alone time together.
Marion Lavorre Edit
- ↑ See "The Ominous March" (1x109) at 0:29:30.
- ↑ See "Critical Role Q&A and Battle Royale: Take II" (Sx10) at 1:21:09.
- ↑ See "Echoes of the Past" (1x38) at 1:01:58.
- ↑ Vax'ildan explains that he enjoys the form of a beautiful woman, and when asked why he limits himself, responds with "who says I do?" See "Trial of the Take: Part 3" (1x20) at 2:05:40.
- ↑ Laura posted about Vex's sexuality on Twitter.
- ↑ See https://www.youtube.com/watch?v=YrT0KQlWqU4&list=PLJO0KXJ_re1Z4PLW3sb1qhFGQKgweNzYR&index=5&t=5597s at 1:32:18 for the full question
- ↑ See "Taryon, My Wayward Son" (1x97) at 1:28:53.
- ↑ See "The Stalking Nightmare" (2x29) at 4:13:55.
- ↑ See "The Journey Home" (2x30) at 1:13:27.
- ↑ See from ep2x76 through 4:33:12.
- ↑ See the interview confirming Mollymauk's gender and sexuality on Twitch.
- ↑ See "Whispers of War" (2x18) at 2:30:10.
- ↑ Mark Hulmes responded to a question from a fan about Calianna's sexuality on Twitter.
- ↑ See "The Stalking Nightmare" (2x29) at 1:20:08.
- ↑ See "Manifold Morals" (2x74) at 3:52:57.
- ↑ Matthew Mercer responded to a question about Bryce's gender on Twitter.
- ↑ See "Family Gathering" (2x71) at 0:24:12.
- ↑ Matthew responded to a question about Dairon's pronouns on Twitter.
- ↑ See "Zemnian Nights" (2x11) at 2:22:47.