The information was therefore delivered via diplomatic pouch and ended up on the desk of Kim Philby. An astonished Philby recognized that he was one of the moles Volkov was about to uncover. Philby insisted in interviewing Volkov himself, instead of leaving that task to an agent in Istanbul. By the time Philby arrived there, however, Volkov had disappeared, presumably executed after Philby notified to the Soviets about the impending defection.

When Igor Gouzinko, a Soviet cipher clerk in Ottawa, Canada defected in September 1945, Philby managed the information so that although a number of Soviet agents were exposed (including Allan Nunn May), he (Philby) was not.

Was awarded the Order of the British Empire in late 1945 for his work in wartime intelligence work, after being nominated by Sir Stewart Menzies.

Divorced Alice Friedman and in 1946 married Aileen Furse with whom he had three children. Was sent during this period of time to Istanbul, Turkey, a hotbed for espionage activity in post-war Europe, serving as acting first Secretary of the Foreign Office In this position, he identified to his Soviet handler, several Albanian nationalists planning to overthrow the communist government in place. The operatives were summarily captured and murdered. Also, worked to foil and British and American invasion of Albania, while at the same time passing along information about Soviet plans for the region. He was commended for his information which was ultimately useless due to its untimeliness.

Was sent to the United States in 1949 to serve as the First Secretary to the British Ambassador in Washington, D.C., acting as a liaison officer between British Intelligence and the CIA and FBI. This placed him in the position of working amongst the elite of the Western intelligence committee. Guy Burgess was also assigned to Washington, D.C. and they two worked together to channel information to Moscow. Met every week with James Angleton, sharing information and coordinating counterespionage efforts.