Proposed is a novel polysiloxane-polyether block copolymer having excellent heat resistance, which is characterized by the molecular structure consisting of repetition of diorganopolysiloxane units and polyoxyalkylene units having a bisphenol linkage of the formula --O--Pn--CMe.sub.2 --Pn--O-- in the unit, Pn being a 1,4-phenylene group and Me is a methyl group. This polysiloxane-polyether block copolymer can be prepared by conducting a hydrosilation reaction between a diorganopolysiloxane terminated at each molecular chain end with a silicon-bonded hydrogen atom and a polyoxyalkylene compound having the bisphenol linkage in the molecule and terminated at each molecular chain end with an alkenyl group or, preferably, allyl group in the presence of a platinum catalyst. The stability of the block copolymer obtained by the hydrosilation reaction can be further improved, when the block copolymer has a silicon-bonded hydrogen atom as the terminal group, by reacting the silicon-bonded hydrogen atom with water or alcohol to be converted into a silanolic hydroxy group or alkoxy group.