The Outkast rapper will portray the legendary guitarist in All Is By My Side, which is currently filming in Ireland.
The film is set in London, and charts Hendrix's pre-fame days in the city while he worked on debut album Are You Experienced?.
However, no Jimi Hendrix originals will feature in the film's soundtrack, as the late musician's estate have refused permission for them to be used.
Instead, Andre 3000 will perform versions of songs that Hendrix covered in the 1960s, reports Rolling Stone.
Songs will include 'Sgt Pepper's Lonely Hearts Club Band' by The Beatles and Muddy Waters' 'Mannish Boy'.
There will also be versions of classic rock hits 'Hound Dog' and 'Wild Thing'.
The recordings were made in Los Angeles with a band of session musicians, including guitarist Waddy Wachtel, bassist Leland Sklar and drummer Kenny Aronoff.
Shooting is expected to finish this week, with a debut set for the Sundance Film Festival. A cinema release is scheduled for early 2013.
Producer Sean McKittrick said: "Andre has been Jimi for four months now. He speaks and walks like Jimi. He dropped a ton of weight. The transformation has been amazing."
In pictures - Andre 3000 as Jimi Hendrix: