Solid bases such as magnesium oxide, calcium oxide, and hydroxyapatite were successfully applied to the reactions of cyanotrimethylsilane with epoxides and oxetanes bearing alkyl substituents and diverse functional groups. The solid base-catalyzed systems were found to induce the ring openings of epoxides and oxetanes much more efficiently and regioselectively, as compared with the conventional, homogeneous acid-promoted systems. The high regioselection is ascribed to a nucleophilic ring opening of a cyanide ion through the coordination of cyanotrimethylsilane to base sites on solid bases.