Syndiotactic polypropylene samples were synthesized under proper conditions using homogeneous catalytic systems based on bis(iminophenoxy)Ti(IV) derivatives and methylaluminoxane. C-13 NMR analysis of the natural abundance end groups suggests that the regiospecificity of propene insertion during the propagation is prevailingly 2,1, although 1,2 insertion is favored in the initiation step. A copolymer of propene with a small amount of 1-C-13-ethene was also prepared with one of the title catalysts, and its stereochemical structure was analyzed by NMR, confirming 2,1 monomer insertion as the main mode of propagation.