The player now has the ability to smith Dragonbone weapons, such as a sword, bow, warhammer, and so on. The new archery weapon introduced in Dawnguard is the crossbow, which comes with plenty of upgrades, as well as the ability to make a dwarven crossbow. I believe there are a few Dawnguard weapons that do extra damage to Vampires, but so far I've only seen a Dawnguard one-handed axe and warhammer. There is also another new weapon, but that weapon has something to do with the main questline, so I won't spoil you.
There are also new spells that can be used.