Producers claim it will explore the "untold story" using information from secret UK government files which will be released on Thursday.
It will dramatise claims that Simpson had an affair with Nazi minister Joachim von Ribbentrop, made by US authorities.
Hollywood star Gwyneth Paltrow is being tipped to play Simpson, the divorced socialite blamed by many for one of the biggest constitutional crises in the royal family's modern history.
Recently-released FBI files suggested Simpson's alleged Nazi connections prevented her marrying Edward while he was monarch.
More records from the Public Records Office, made public on Thursday, are expected to shed light on the Nazi links and events surrounding the abdication.
Provisionally titled The American Woman, the BBC says Shakespeare In Love star Paltrow is being considered for the film, but that no casting decisions have been made.
"
There are many gaps in our understanding of Wallis Simpson and Edward VIII - this is the last piece of the jigsaw
"
Heidi Thomas
Screenwriter
"The American Woman is an ambitious event drama which will provide a fresh insight into the first major constitutional crisis that the royal family faced in the 20th Century," BBC controller of drama commissioning Jane Tranter said.
"In addition to the FBI papers published last year, the release of secret government files on Thursday will provide a new perspective on what happened in such a momentous period - both for the royal family and for Britain in the lead-up to World War II."
It will be written by Heidi Thomas, who wrote the screenplays for Madame Bovary and I Capture The Castle, and directed by Simon Curtis, who directed TV versions of Man and Boy and David Copperfield.
Hit series
The American Woman follows the success of another BBC One royal drama The Lost Prince, which was watched by more than eight million people when it concluded on Sunday.
Ms Thomas said: "There are many gaps in our understanding of Wallis Simpson and Edward VIII, because of the secrecy surrounding them. This is the last piece of the jigsaw."
A hit TV mini-series about the relationship, Edward and Mrs Simpson, was shown on ITV in 1980.
It starred Edward Fox as King Edward and Cynthia Harris as Wallis Simpson.