Divinities
TimeLord (Saga Frontier) vs. Shinryu (Final Fantasy 5): Shinryu's first turn may or may not go before TimeLord, but it really doesn't matter since he skips it... Tidal Wave is used on the second. Which beats out unhasted average speed, but yeah, auto-haste or masamune both let you go first. So!
Ryu3 (Breath of Fire 3) vs.
Belial (Wild Arms 4): 4D Pocket.
Ghaleon (Lunar) vs. Viola (Radiant Historia): Attack -> Hell Wave breaks the barrier while doing some damage, Viola's offence isn't special enough to blitz Ghaleon.
Zophar (Lunar 2) vs.
Yuna (Final Fantasy X): Oh look, Yuna gets to beat both Lunar final bosses, how amusing.
Demigods
Berle (Star Ocean 2) vs. Wugui (Shadow Hearts): Durability.
Millenia (Grandia 2) vs.
Yaridovich (Super Mario RPG): Easily survives whatever nonsense Millenia can do with one SBE. This assumes he just doesn't go first and OHKO her. Which he probably does.
Jack van Burace (Wild Arms) vs. Wakka (Final Fantasy X): Useless in-game status beats useful in-game status, elves cringe.
Jowy Atreides (Suikoden II) vs. Jessica Albert (Dragon Quest 8): Who goes first depends on what equips you use in the averages. Angelo apparently uses Kaswoosh as his DL damage, so he should have Mercury's Rapier, which is all that matters here to make Jowy faster. If someone wants to argue why Angelo should have another weapon as a default, I'll change my vote.
Fang (Final Fantasy XIII) vs. Gades (Lufia series): Har.
Raquel (Wild Arms 4) vs. Legretta (Tales of the Abyss): Legretta has some advantages over both Sync and Van as duellers (durability for starters). Her disadvantage? Failing forever until below 75% HP.
Magus (Chrono Trigger) vs.
Ryu Bateson (Breath of Fire 2): Magus might survive G. Dragon! Doesn't matter.
Purim (Secret of Mana) vs.
Dorothy Gale (The Wizard of Oz): dat sleepblocker stat hit
Heroes
Lyon (Fire Emblem: The Sacred Stones) vs.
Ashley Winchester (Wild Arms 2): Much as I dislike voting this way, Lyon has no damage control and isn't OHKOing, so is giving Ashley a fuckton of FP. Ashley waits first turn, gets 75 FP, uses Full Clip.
Marle (Chrono Trigger) vs. Freya Crescent (Final Fantasy IX): Hilariously Marle might win even if berserked, stop
is that badass (IIRC it's over 10 turns or something insane). Not sure if status immunity blocks berserk or not in CT. Of course, if she DOES stop berserk, this match is so over.
Eiko (Final Fantasy 9) vs.
Lazlo (Suikoden IV): Faster, ID.
Sara (Breath of Fire) vs. Rune Walsh (Phantasy Star IV): ....
Yeah Rune has two good shots of damage but that's it.
Eruca (Radiant Historia) vs.
Princess Toadstool (Super Mario RPG): Faster, 2HKOs with Frying Pan or something. Don't think her silly shield move works well when slow?
Alfina (Grandia III) vs. Tengaar (Suikoden series): I think?