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The 2 letters P and K stand for: Player Kill.
PK'er would be Player Killer.
More than one PK'er would be: PK'ers.

Basically a PK'er is a person who character's sole perpose is to kill other people's characters, for whatever reasons. It can happen in almost in game that let's 2 or more characters go head-to head or duel as some may call it.

Comes from the old style short hand typing inside closed realms of the online game Diablo and/or Diablo 2 LoD.
These damn Pk'ers bitches are kicking my ass.
PK'er by John pk'er August 14, 2007
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From online games, deriving from "Player Killing". A PKer is one who kills other players for the enjoyment of killing them or causing them grief. See also RPK or RPKer.
Watch out for Riv when you get in Diablo, he's a known PKer.
pker by [LK]Myrik December 10, 2004
Related Words
The abbreviation "pker" stands for "player killer" and is most commonly used in online games where players fight one another head-to-head, such as Diablo and Runescape.
In Runescape: "Watch out for pkers when you go in the wilderness!"
pker by Litza Karpov September 30, 2005
09 Pker: Catastrophic failures that have the e-balls to call themselves "pk'ers," but rely on the amount of brews their pokemon can hold, and act e-tough because they sit on the computer long enough to spam click something 50,000 times a second.
Damn, you see that 09 pker? His left hand must be down his pants while his right is on the mouse!
09 Pker by ILikeButter August 29, 2009

Ancient pkers 

Ancient pkers is one of the best pking clans in runescape, they owned the wild, and now they own bh.
Ancient Pkers owns frozen fury
Ancient pkers by No way out March 4, 2008
Symptom:
A PKer is someone who hunts less experianced players on internet videogames. PKer's are considered the murderers in the RPG universe. Usually, a PKer will target someone who is grossly lower in level then they are, if it is an RPG that is. PKers have zero remorse for who they kill, and will eliminate one or more of the same players over and over again. In the popular game, Diablo 2, PKers run rampant in hardcore. There are a few in softcore, but not as many.PKers will get more "pleasure" from killing in HC, due to how once their victim is dead; It stays dead for good. Because of this lovable trait, PKers are rarer in softcore, but still should be looked out for! Pkers will use hacks from time to time to improve their "kill rate". Lagging the game, etc.

Cure:

Usually a PKer is focused on killing weaker people then him, so it's fairly easy to dispose of one with the conventional means.(i.e killing him.)
Pkers will usually, if alone, leave the game if they are outnumbered, or see that they will lose the fight. Pkers who are also skilled fighters are difficult to find- but still exist nonetheless.
(The Pker)Lixterian: hey can i join ur party?
Bob_LOLZ: k, plz helpy us kill d thx?
Lixterian: k
*They arrive at Chaos Sanctuary*
Lixterian: brb, i got 2 repair my sheild
Bob_LOLZ: k
Lixterian has declared hostility towards you.
Bob_LoLZ was slain by Lixterian.
noob was slain by Lixterian.
cocksucker was slain by Lixterian.

cocksucker: WTF FAG FUYCK!!11 I TRUSTED U FAG
Lixterian: :)
pker by Ted_Bundy December 26, 2005

2011 Pker 

A limpdick cocksucker who ventures into PvP in RuneScape who falsely label themselves as good because they spend countless hours asking friends for bots, and countless hours using them, just to get some gay-looking sword. This generation of inbreds is the worst to plague RuneScape, one mother's credit card at a time!
Typical 2011 Pker:

Fuck friends man, my mom gave me her paypal information. All these DDawS programs I can buy now to get these electronic gold pieces! You can call me Super Faggot.
2011 Pker by Hluah August 22, 2011