The news was announced first on the actress's official Twitter page and later confirmed through a statement from Bond movie producers Michael G. Wilson and Barbara Broccoli.
Eunice Gayson, the first ever Bond Girl, has passed away aged 90.
"Our honest thoughts are with her family", the pair said.
Eunice Gayson leaves behind a daughter, Kate, who had a brief cameo in the 1995 Bond film GoldenEye.
From left, Tania Mallet, Eunice Gayson and Britt Ekland at a photocall for Bond 50 on Friday, Sept. 21, 2012 in London, UK.
Gayson had originally been cast as Miss Moneypenny before the producers made a decision to replace her with Lois Maxwell and recast Gayson as a femme fatale character.
She became the first person to ask for James Bond's name in the movies after her character met the suave spy at a card table in 1962's Dr. No, allowing Connery to utter 007's signature line: "Bond". She will of course be forever immortalised for her part in the James Bond films in the role of Sylvia Trench.
Born in 1928 in Surrey, England, Gayson made stage appearances in "Born Yesterday", "No, No Nanette", "The Sound of Music", and in British TV revues.
"I admire your courage, Miss, uh...?"
"[Director] Terence Young told me to take him away for a drink - even though he was meant to be on the wagon - so I took him off for a drink or two and he came back on set and said: "Bond, James Bond".
Eunice played the same Bond girl in the 1963 follow-up flick, "From Russia with Love", as well.