Polymerization of propene at -78 degrees C in the presence of a homogeneous catalytic system based on a Ni(II) diimine derivative and methylaluminoxane affords prevailingly syndiotactic crystalline poly(propylene) (rr triad content approximate to 80%). C-13 NMR analysis of the polymer microstructure indicates that the stereochemistry of the monomer insertion is controlled by the configuration of the methine carbon of the growing chain end (unlike-1,3 asymmetric induction). This is the first example of stereospecific homopolymerization of propene promoted by a late transition metal catalyst.