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Lilith's unlocks on average are my pick for best of any character.
Satanic bible and maw of the void are also great. Demon baby is one of those items you'll likely regret unlocking later on when it shows up in place of other potentially better devil deals over and over, but it's not terrible.
In approximate order of my opinion on their quality:
Incubus is the best familiar. I do not think anyone can argue with that. It's basically a hard to aim 20/20 that gets slightly different synergies from certain items than normal tears.
Serpent's kiss is one of the best items for keeping yourself alive in the game, and it also gives you a small increase to dps thanks to the occasional poison effect. When I have tears that work with serpent's kiss, I leave the hush fight with more health than that with which I started every time.
Succubus is amazing for room clearing AND helps your damage. Also one of the best familiars.
Rune bag is my pick for best bag. I know that one's debatable, but that's my opinion on the matter. The fact that you can get it from gold chests is pretty awesome.
Box of friends is amazing if you have good familiars, and it spirals out of control during boss rush and greed mode.
Cambion conception is better if you get it early on in your run, but it has the potential to be incredibly good if you do, and once you unlock it lilith STARTS WITH IT.
Euthanasia (you'd have to beat delirium for it) is ok. Not sure if it's particularly good overall due to how rare the fire rate is (synergizes with things that boost firing rate and luck), but it's a lot of fun, and it helps toward getting the spun transformation.
All of her unlocks are good or great.
As for Lilith, each of her unlocks are great items, except maybe Duality, but I'd go for Serpent's Kiss and Succubus first, as you can get them both in the same run.
It's alright. I like it as the lost since it guarentees devil deals even if you haven't locked them in, or if you need key pieces because you're trying for mega satan or delirium and are too slow/vulnerable for the hush fight to guarentee void. It also gives you a backup plan if you unlock a devil deal but don't have the hearts to spare, so you can do angel instead. Not sure it's worth spending a heart on from a devil deal to get it much of the time though.
Nail
stanic bible
Abbadon
Maw of the Void
Are good unlocks from Az, some say Daemon's Tail is a great unlock but its never been impressive for me in a run.
Abaddon is probably azazel's best unlock other than lilith, in my opinion. The damage + the fear + the huge pile of sin health is an outrageous bargain, and it immediately gives you polaroid/negative synergy. There are a small number of cases where you might not want it, but I've never entered a room, seen abaddon and been sorry to take it, except during intended mega satan runs.
The daemon's tail is really weird.
It decreases the odds of any hearts turning up at all (which means you'll usually get other things besides hearts from sources that can pay out with hearts), but boosts the odds of sin hearts relative to other hearts.
I have had good runs with it, but I often end up regretting carrying it around at some point, since it does drop the odds of getting soul hearts by a LOT.
If you enter a devil deal with the keeper and take Abaddon...you'll experience instant regret