Deadshot - created by Bob Kane, David Vern Reed and Lew Schwartz - first appeared in 1950 comic Batman #59.
Canadian actor Rowe will make his debut as the character in Arrow's third episode, titled 'The Lone Gunman'.
"Deadshot doesn't speak much, so he has to have that physicality," exec Marc Guggenheim told TV Guide. "And Michael certainly has that - he has that look."
The producer added that it is "very possible" that the character will return to battle Arrow (Stephen Amell) in future episodes.
Katie Cassidy (Gossip Girl) will also star in Arrow as Dinah 'Laurel' Lance - also known in the comics as Black Canary - while Guggenheim has encouraged fans to "watch very carefully" for possible appearances from further DC Comics characters.
The series premieres on October 10 on The CW in the US. Sky1 will air Arrow in the UK.
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Watch a clip from the Arrow pilot below: