This paper discusses a new family of syndiotactic polystyrene (s-PS) derivatives containing the amino group, including poly(4-aminostyrene); poly(4-aminomethylstyrene), and poly(4-aminoethyl-styrene). These semicrystalline polymers exhibit high melting temperatures (similar to 350 degrees C) and relatively fast crystallization rates. These functional syndiotactic polymers are prepared in two steps. Syndiospecific polymerization of a styrene derivative containing a masking N,N-bis(trimethylsilyl)amino group is achieved by using a half-sandwich titanocene/perfluoroborane catalyst system. This study focused on the catalyst system (catalyst and cocatalyst) that can polymerize functional monomers with high catalyst activity and syndiotacticity. Acid hydrolysis leads to the complete recovery of primary amino groups in s-PS derivatives.