Sinestro:

1st Appearance: Green Lantern (vol. 2) # 7 (August 1961)

Parallax:

1st Appearance: Green Lantern (vol. 3) #50 (March 1994)

Nekron:

1st Appearance: Tales of the Green Lantern Corps #2 (June 1981)

Atrocitus:

1st Appearance: Green Lantern (vol. 4) #25 (December 2007)

Agent Orange: Larfleeze:

1st Appearance: Green Lantern (vol. 4) #25 (Dec. 2007)

The Manhunters:

1st Appearance: Justice League of America (vol. 1) #140 (March 1977)

The Qwardian Weaponers:

1st Appearance: Green Lantern (vol. 2) #2 (Oct, 1960)

Mongul:

1st Appearance: DC Comics Presents #27 (Nov. 1980)

Superboy-Prime:

1st Appearance: DC Comics Presents #87 (November 1985)

Cyborg Superman:

1st Appearance:
As Hank Henshaw:
Adventures of Superman #465 (April 1990)
As Cyborg Superman:
Adventures of Superman #500 (June 1993)

Krona:

1st Appearance: Green Lantern (vol. 2) #40 (October 1965)

Star Sapphire:

1st Appearance: All-Flash Comics #32 (Dec 1947/Jan 1948)

The Anti-Monitor:

1st Appearance: Crisis on Infinite Earths #2 (May 1985)

Arkillo (Sinestro Corps Member):

1st Appearance: Green Lantern (vol. 4) # 10 (May 2006)

Hector Hammond:

1st Appearance: Green Lantern (vol. 2) # 5 (March-April, 1961)

Black Hand:

1st Appearance: Green Lantern (vol. 2) #29 (June 1964)

Evil Star:

1st Appearance: Green Lantern (vol. 2) #37 (June 1965)

Darkseid:

1st Appearance: Superman's Pal, Jimmy Olsen #134 (December 1970)

Kalibak:

1st Appearance: New Gods (vol. 1) #1 (March 1971)

Desaad:

1st Appearance: Forever People (vol. 1) #2 (May 1971)

Grayven:

1st Appearance: Green Lantern (vol. 3) #74 (June 1996)

Dr. Polaris:

1st Appearance: Green Lantern (vol. 2) #21 (June 1963)

Shark:

1st Appearance: Showcase #3 (July-August 1956)

Sonar:

1st Appearance: Green Lantern (vol. 2) #14 (July 1962)

Goldface:

1st Appearance: Green Lantern #38 (Summer 1965)

Amon Sur:

1st Apperance: Green Lantern (vol. 3) #162 (June 2003)

Lord Malvolio:

1st Appearance: Action Comics #632 (December 1988)

Solomon Grundy:

1st Appearance: All-American Comics #61 (October 1944)

Vandal Savage:

1st Appearance: Green Lantern (vol. 1) #10 (Winter 1944)

Blackbriar Thorn:

1st Appearance: DC Comics Presents #66 (February 1984)

Harlequinn (Golden Age):

1st Appearance: All-American Comics #89 (September 1947)

Fatality:

1st Appearance: Green Lantern (vol. 3) #83 (February 1997)

Effigy:

1st Appearance:
As Martyn Van Wyck: Green Lantern (vol. 3) #110
As Effigy: Green Lantern (vol. 3) #113

Alex Nero:

1st Appearance: Green Lantern (vol. 3) #132 (January 2001)

Major Force:

1st Appearance: Captain Atom (vol. 3) #12 (February 1988)

The Sinestro Corps:

1st Appearance: Green Lantern (vol. 4) #10 (May 2006)

The Red Lanterns:

1st Appearance: Green Lantern (vol. 4) #25 (December 2007)

The Black Lanterns:

1st Appearance: Green Lantern (vol. 4) #43 (September 2009)

The Weaponer:

First Apperance: Green Lantern Corps (Vol. 2) #49 (June 2010)

Invictus:

Green Lantern: New Guardians #5 (January 2012)

The Third Army:

First Appearance: Green Lantern Annual #1 (August 2012)

Volthoom: The First Lantern:

First Appearance: Green Lantern Annual #1 (August 2012)

The Lantern's need more femme fatale's.

I agree for a title that crosses all of space, you would think it would be a little less of a sausage fest

I own three of those first appearances; Darkseid, Blackbriar Thorn and Major Force. Except that was in Captain Atom Annual #1.
http://www.comiccollectorlive.com/LiveData/Issue.aspx?id=736c0d25-2b8f-45e6-a04a-59db34813866

Got my info from the DC Wiki. Which I think is right and CCL is wrong because the CCL entry says that annual is 1987, when my copy says 1988. But I'm haven't read this issues in many, many years. So I could be wrong, and it might be time to re-read it.

i hope in this new 25 universe they bring back Amon Sur! he was a awesome villan one of my favorites.

Updated:

-The Weaponer
-Invictus
-The Third Army
-The First Lantern