The 64-year-old 'Avengers' actor will star alongside Colin Firth in Vaughn's latest comic book adaptation, which is based on Mark Millar and David Gibbons' super-spy graphic novel series, according to Variety.
Jackson will play the main antagonist to Firth's expert secret agent and his young rookie protege, is to be played by newcomer Taron Egerton.
Vaughn, who previously directed another Millar comic book adaptation, 'Kick-Ass', as well as 'X-Men: First Class', has been eyeing a big Hollywood name for the role, and previously offered the part to Tom Cruise and Leonardo DiCaprio.
Vaughn co-wrote the script with his regular collaborator Jane Goldman - who co-wrote 'Stardust' and 'Kick-Ass' with him - and he will produce as well as direct through his Marv Films production company.
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The film's leading lady is yet to be decided and producers are keen on 'The Bling Ring' and 'Harry Potter' star Emma Watson, but are also considering 'Dark Shadows' actress Bella Heathcote.
Jackson is currently filming Marvel comic book movie, 'Captain America: The Winter Soldier', reprising his role as SHIELD leader Nick Fury. He will again play the role in 'The Avengers: Age of Ultron', which will be filmed next year for release in 2015.