Strong Bronsted-base-catalyzed addition reactions of alkylazaarenes with vinylsilanes are reported. The reactions of alkylpyridines and their analogues with vinylsilanes proceed in moderate to high yields in the presence of catalytic amounts of LiTMP, LiCl, and MS 4 angstrom. This is a general method that can be applied to catalytic addition reactions of alkylazaarenes with vinylsilanes.