The 30-year-old two-time world champion clocked a best lap of one minute and 17.192 before a rain shower - and a red flag -- interrupted the afternoon's running to wind up seven-tenths of a second quicker than Mercedes team-mate and nearest title rival Nico Rosberg of Germany.
Rosberg, who is seeking to complete a rare hat-trick of three successive Monaco Grand Prix wins, had a 'moment' during the morning when he 'kissed' the barriers at Tabac corner and was unable to mount a serious challenge on the impressive Hamilton.
Dutch teenager Max Verstappen continued his extraordinary impact this season by taking seventh in the second Toro Rosso car ahead of a much-improved performance from two-time champion Fernando Alonso of Spain in the troublesome McLaren-Honda.
German Nico Hulkenberg was ninth for Force India and Frenchman Romain Grosjean 10th in the Lotus.
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