Depends on how you view her matching Ventress. She's stated by Quinlan Vos to be great at teamwork, though, which is obviously beneficial for this matchup: "Her lightsaber skills were impressive. In battle, her movements were focused and precise, flowing from one to the other. All Jedi are my brothers and sisters, but only with a few, like Luminara Unduli, do you intuitively mesh."
Luminara isn't a non factor but she's well below Maul. Prime Qui-Gon might stalemate TPM Maul IMO, so if it's TCW or Rebels Maul he wins a large majority.
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Luminara was pretty alright against Ventress while half-blind. Can't say she and Qui-Gon would stomp; it's pretty close. I can be persuaded either way.
__________________ "Technology equals might!" "Evolve or perish"
Luminara was below the likes of Ki-Adi Mundi, Shaak Ti etc. in sabers
__________________ ''It is necessary that I should die for my people; but my spirit will rise from the grave and the world will know that I was right." The Almighty Führer
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Luminara would seem to have a weakness against the unorthodox fighting style of Maul as she did with Ventress. She did not lose against the latter because of inferior dueling or force ability, but rather because she was unprepared against Ventress's surprise attacks which took advantage of the environment. This is exactly what Maul did to Qui-Gon and Kenobi.
The small details add up; Luminara's ultra-conservative dress, the lack of attachment to her padawan, the professional way she interacts with everyone, etc. suggests she's a very traditional jedi. Not necessarily a bad thing, but not an efficient mind-set for fighting users like Maul who are trained to defeat run-of-the-mill jedi. Go ahead, call me an idiot or whatever joker.
__________________ "Technology equals might!" "Evolve or perish"
I actually agree with that, more or less. But I've always held the viewpoint that Luminara very likely learned from her experience with Ventress, so she'd be more cautious and less likely to underestimate her opponents in the future.
One thing though; Luminara is actually quite attached to Barriss, but she puts up a facade.
I doubt that replacing Kenobi with a noticeably better combatant would make the duo less effective even if sacrificing synergy. And even still, Luminara is a fantastic team player regardless.