<p>An organopolysiloxane gum is prepared by polymerizing a cyclic organopolysiloxane with a low molecular weight linear organopolysiloxane end-blocked with a triorganosilyl group in the presence of a thermally decomposable catalyst. After the polymerization reaction, the catalyst is deactivated by heating the reaction product under a subatmospheric pressure of typically up to 500 mmHg.</p>