You mean aside from the upcoming stuff (Doctor Strange, Black Panther, Captain Marvel, Inhumans)?
I guess both Ghost Rider and Blade can be considered major characters. Maybe throw in Moon Knight as well.
On a cosmic level we're still missing Nova, Adam Warlock and I guess Phyla-Vell (aka Quasar, aka Martyr) and Moondragon.
The Asgard side is missing Brunnhilde and Angela
off the top of my head. And then there's off course the Greek pantheon.
I am not sure what the legal situation is there but Jessica Drew aka Spider-Woman is a separate character from Spider-Man and pretty important as well.
Blue Marvel has a pretty prominent role in the new Ultimates run. Same with Monica Rambeau, currently going by the name Spectrum.
Tons of characters left tbh.
Also, describing She-Hulk as "a girl version of Hulk" doesn't even begin to do her justice.