A new general functionalization method (GFM) of synthesizing α-functionalized polymers has been developed. α-Vinyl-functionalized polystyrene was obtained by anionic polymerization of styrene using 4-pentenyllithium as an initiator. Chloromethyldimethylsilane-functionalized polystyrene was successfully synthesized from vinyl-functionalized polystyrene by hydrosilation using Karstedt's catalyst. Nucleophilic substitution of this polymer was carried out in presence of pyrrolidine to obtain α-pyrrolidine-functionalized polystyrene. α-Triethoxysilylpolystyrene was obtained by hydrosilation of a-4-pentenylpolystyrene with triethoxysilane using Karstedt's catalyst.