My personal choices
1. Benoit's WWE theme (Whatever by Our Lady Peace)
That riff in the song is amazing, it's got kind of a hollow, shrill sound that just instantly evokes a sense of danger. At the same time, once the riff cuts out and the vocals come in it was somewhat laid back, showing that it wasn't a big deal for him to kick your ass.
2. RVD's WWE theme (One of a Kind by Breaking Point)
The song itself isn't all that great because the verses are meh, but the chorus is very high energy and the lyrics fit RVD being one of a kind. I also love the starting bit, with that deep, rolling sound. The chanting part with the people just going "Hey! Hey! Hey!" is pretty awesome too.
3. Goldberg's theme
That song suits Goldberg so well. It's an epic sounding instrumental with the thundering drum beat, it's just like a marching song. That music sounds badass, in a lot of ways moreso than any heavy metal theme that's been used because it's different and like I said, it just soundss epic.
4. Edge's current theme (Metalangus by Alter Bridge)
Sure, Alter Bridge is just Creed with a new singer, but they are an awesome, heavy hard rock band. Anyways, this song just sounds great, it`s got that energy and almost urgency that Edge always has, but at the same time it`s a confident song that goes along with Edge`s cokciness. The intro (which, as another poster noted, is actually the song`s outro) with the furious drums and guitar, are an amazing attention grabber when the entrance starts.
5. Brock Lesnar`s WWE theme
See what I wrote about Goldberg, and just apply it here.