I've been trying to give her some new armour and the like and she doesn't seem to want to wear it over her default armour.
Is there a trick to getting her to equip items? Armour specifically? If I can't upgrade her gear I'll go back to using Mjoll.
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Serana is capable of wearing both light and heavy armor, but the armor must be an upgrade over her default gear for her to equip it. From her appearance, I'd guess that she is already equipped with the female version of the Royal Vampire Armor. She will also equip enchanted rings, amulets, circlets, and some weapons.
I've found that can equip Serana with about any armor that you want (including custom armor in the Steam workshop). Usually it has to be a higher rating, but from the console you can
removeallitems 0 to drop the vampire armor. Once that is done you could
openactorcontainer 1 and put into the inventory whatever armor you want the follower to wear. I found a good example of Serana with custom armor (along with some other followers):
She'll only wear snow elf armor that you can get during the quest for Auriel's Bow from the evil brother hiding the bow. As far as any other apparel she'll wear anything you give her. It's interesting because the snow elf armor is only about an 81 rating after improving, whereas other armors can be improved much higher. This is true only without mods/console, of course...