There are many apocryphal stories as to when Moore's name was first dropped as a possible candidate for the role of James Bond. Some sources, specifically Albert R. Broccoli from his autobiography When The Snow Melts, claim that Moore was considered for Dr. No, and that he was Ian Fleming's favourite for the role after apparently having seen Moore as Simon Templar in The Saint; however, this story is often debunked by fans and Bond-film historians, who point to the fact that the series did not begin airing in the United Kingdom until October 4, 1962 – only one day before the premiere of Dr. No.

Other sources, such as the insert for the special edition DVDs, claim that Moore was passed over for Bond in favour of someone who was older. As Moore is older than Sean Connery, this is probably not true. Publicly, Moore wasn't linked to the role of 007 until 1967, when Harry Saltzman claimed he would make a good Bond, but also displayed misgivings due to his popularity as Simon Templar. Nevertheless, Moore was finally cast as James Bond in Live and Let Die (1973).

Roger Moore's seven years as Simon Templar earned him enough popularity (and credibility) among fans of detective fiction to earn many Bond fans' acceptance, despite the inevitable comparisons to Connery. Moore played Bond in:

To date, Moore is the longest-serving James Bond actor, having spent twelve years in the role (from his debut in 1973, to his retirement from the role in 1985), and made seven official films. (Connery also made seven, but his last Bond film, Never Say Never Again (1983), is not part of the official EON Productions series.) He is also the oldest actor to play Bond: he was 46 when he debuted, and 58 when he announced his retirement on December 3, 1985, as it was agreed by all involved that Moore was too old for the role by that point. Moore himself was quoted in the contemporary press as saying that he felt embarrassed to be seen doing love scenes with beautiful actresses who were young enough to be his daughters.