Vocals, more than anything else, is NOTHING about your technical ability. You need so much more than a pretty voice.
Guys:
Glenn Danzig (Misfits, Samhain, Danzig): Glenn has one sexy, sexy howl. I mean fuck, 'Killer Wolf' is maybe the most erotic song ever. It could probably turn the whole 700 club gay, then 'Wicked Pussycat' could knock 'em straight again.
Rob Halford (Judas Priest): Often copied. Never bettered. The Tipton/Downing guitar assault is legendary, but stick them with Rob 'my trousers are so tight I've gone backwards through puberty' Halford, and fucking hell...
Quorthon (Bathory, Silverwing): Just...epic. Hail to a fallen brother.
Kristoffer 'Garm' Rygg (Ulver, Arcturus, Borknagar, etc.): The band list says it all. It's the diversity of Garms output that's the real killer. My favourite garm moment? ANANGELCAMETOMEANDSAIDOPITYTHEFOOLISHYOUNGMAN. OHORRIBLEODREADFULSTATE, CONSIDERTHEBURNINGDUNGEONTHOUARTPREPARINGFORTHYSELFFORALLETERNITY!
Bernd Seeberger (Cryptic Wintermoon): Possibly the only guy in the whole symphonic black/dark metal scene who can actually inject some fucking emotion into his vocals and not just be a cookie monster. Just listen to 'When Daylight Dies' or 'Into Ashes'. Good clean vox too.
Peter Steele (Carnivore, Type O Negative): Another voice which is, frankly, just fucking sexy. It's all those orgasmic moans, like he's so goth it is actually literally hurting him.
Dave Tibet (Current 93): At times, Tibets vocals can get so fragile you think he might break, then suddenly he will envelop you in a monstrous, spitting intensity, or just scream for 30 seconds without taking a breath. Great.
Varg 'Count Grishnack' Vikernes (Burzum): One thing Varg definitely understood was what BM vocals were about. On 'Burzum' He sounds like he's being tortured under four feet of ice. Awesome.
Tony Wakeford (Sol Invictus, L'Orchestre Noir, etc.): Wakefords singing has a simple, raw, emotional honesty that just cannot be cultivated.
Martin Walkyier (Sabbat, Skyclad, The Clan Destined): Martins best stuff is the Sabbat/Early Skyclad stuff, probably peaking on Wayward Sons of Mother Earth. It's a combination of his monstrously fast thrash vocals, the Shakespearean exactness of his delivery and his obvious sheer love of the English language. He's also the greatest lyricist of all time.
Gals:
Diamanda Galas: Needs no introduction. This lady could disembowel Chuck Norris and 100 ninjas just by singing 'Swing Low Sweet Chariot' at them.
Angela Gossow (Arch Enemy): Anyone ragging on Gossows vocals is just a fucking sexist. Her style is somewhat unique, definitely feminine, but definitely DM, with a wonderfully sick, diseased sounding edge.
Elizabeth Fraser (Cocteau Twins): The late 80's stuff is basically just pure vocal acrobatics.
Lisa Gerrard (Dead Can Dance): I can think of very few people with a voice powerful enough to carry a song alone, a-capella. This explains why DCD's 'The Wind That Shakes The Barley' is one of my favourite tracks of all time.
Liv Kristine Espenæs (Theatre of Tragedy, Leaves Eyes, Atrocity, etc.): Liv Kristine is just...well, Liv Kristine. The original beauty off-setting beast vocals. The fact that she's left ToT basically means that they will never be good again, not that I was holding out much hope for that anyway...
Stine-Mari Langstrand (Lumsk): Now, this is how your classically trained stuff should sound, people. Tarja Turunen, I'm looking at YOU. Her higher register is absolutely wonderful.
Rose McDowall (Strawberry Switchblade, Current 93 etc.): McDowall's just fucking haunting. And I do have something of a thing for Scots and Irish vocals. Seriously though, the intro to 'Black Flowers Please' off of Cats Drunk on Copper...sends shivers down your spine it does.
Kari Rueslåtten (The 3rd and the Mortal, Storm): She's a pussy for kicking up a fuss about singing brutal lyrics for Storm, but her work definitely makes up for it. Very strange, jazzy sort of stuff. I love her uncomfortable sounding choral singing on tracks like 'Sophisticated Vampires'. Also, not that it should be a consideration, she's so hot it hurts.
Other:
Anna-Varney Cantonadea (Sopor Aeternus & The Ensemble of Shadows): I can't imagine a better darkwave vocalist than Anna-Varney. Melodramatic to the point of absolute absurdity, shrieking, groaning, wailing, whispering, sobbing... you can practically hear the tombstone, veil and the hand draped across the forehead.