The solvent effect on the cyclic compound formation in the base-catalyzed aminolysis reaction of room temperature vulcanized polydimethylsiloxane networks under ambient temperature was investigated. The complete dissolution time of the silicone rubber in the less polar solvent system was longer which is attributed to the internal diffusion resistance for the penetration of the activated nucleophiles in the inherent hydrophobic polysiloxane networks. The main products were cyclic oligomers in the polar solvent systems. The reaction rate of aminolysis was proved to be faster than that of alcoholysis with the aid of a model compound under the reaction conditions designed.