Fleming's life is being dramatised for Sky Atlantic and will be screened later this year, the Daily Mail reported.
'Mamma Mia!' star Dominic Cooper will portray Fleming onscreen.
Pulver will play Ann, a society figure who was Viscountess Rothermere for several years and was later married to Fleming for 12 years, until his death in 1964.
"I am thrilled to be playing Ann, a real life high society siren worthy of Fleming's finest fictional femme fatales.
"In extraordinary times Ann had the ear of politicians as powerful as Churchill and counted artists like Lucian Freud among her friends, yet was consumed by a torrid romance with the great Ian Fleming - a twisted and passionate love that would last the rest of their lives," said the actress, who has previously starred in 'Sherlock' and 'Spooks and Robin Hood'.
The biopic will also feature Anna Chancellor as Lieutenant Monday in Naval Intelligence, who is thought have been the model for Moneypenny.
Samuel West will play Admiral John Godfrey, who may have been the inspiration for Bond's boss M.
The new series, which has a working title of Fleming, is to be filmed in the UK and shot on location in the United Kingdom and Budapest, Hungary.
