The Dylan Thomas love triangle drama stars Keira Knightley, Sienna Miller, Matthew Rhys and Cillian Murphy.
Maybury is expected to attend the gala with Knightley, Miller and Rhys.
Knightley's mother Sharman Macdonald wrote the script. Producers are Rebekah Gilbertson and Sarah Radclyffe with co-producers Huw Penallt Jones and Bill Godfrey and executive producers David Berstein, Linda James, Hannah Leader, Joe Oppenheimer, Tim Smith and David M Thompson.
The film will be eligible for EIFF's Michael Powell Award, PPG Award for Best Performance in a British Film, and the Standard Life Audience Award.
Festival artistic director Hannah McGill said: 'I couldn't be happier to be opening this most auspicious Festival with this utterly seductive and fascinating film, which stars some of the most charismatic young performers in the business, and affirms John Maybury as one of our most important directors. It's film that I personally adore, and opening with it is the perfect expression of our commitment to intelligent, impassioned, exciting new filmmaking.'
Maybury added: 'I am thrilled and honoured to have the film at the Edinburgh Film Festival. I have a deep affection for the Festival since they were so good to award Love Is the Devil the Michael Powell Award and Derek Jacobi and Daniel Craig, Joint Best Actor Awards ten years ago'.
Lionsgate UK opens The Edge Of Love in London on June 20 followed by a UK rollout on June 27.This year's Edinburgh festival moves from its traditional August slot to June 18-29.
The full programme will be announced on May 7.
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