Ofcom made the ruling after receiving two complaints that the ad, which described Blair's time in power as a "missed opportunity", was political advertising. It also emerged that the ad had not been approved by the Radio Advertising Clearance Centre before it was broadcast.
The section that caused problems was: "Blair: A modern tragedy. The definitive guide to the missed opportunity of the Tony Blair era. Manipulator, communicator, fabricator. Only in The Spectator."
GCap, owner of Classic FM, confirmed that the ad had not been approved by the RACC, and said that it had reviewed its internal procedures for clearing ads, and would ensure that scripts submitted for '"special categories" of ads were submitted for clearance in future. Ofcom welcomed the move, but found that the failure to clear the ad was a clear breach of its code.
Separately, ITV1 Saturday evening favourite 'Harry Hill's TV Burp' has also fallen foul of Ofcom regulations.
Ofcom received 44 complaints over a scene that used footage from Channel 4's 'Born Survivor', showing the ex-SAS man Bear Grylls biting the head off a live frog, and roasting a turtle, which appeared to be alive, in its shell over a fire.
People complained that the scene had upset them and their children, and questioned whether it was appropriate to use such clips for humorous effect.
Producers defended the show, saying that Harry Hill's sense of humour had been well established in previous series and also argued that the original footage could have been seen before the watershed and was, in fact, broadcast at a similar time to 'TV Burp'.
However, Ofcom ruled that because 'Born Survivor' was more educational and less of an entertainment programme, there was more awareness that such scenes might appear.
It said: "In Ofcom's view, the choice of clips required more careful consideration when broadcast in a light entertainment programme during early peak time on a Saturday evening on ITV1.
"Given the longstanding popularity of 'Harry Hill's TV Burp' with families and young viewers, and taking into account the potentially high number of children available to view the programme at this time, Ofcom found that the clips were inappropriately scheduled."