Cp*TiCl2(L) [L = C3H3N2 (1), 3,5-Me2C3HN2 (2) and 3,5-(Pr2C3HN2)-Pr-i (3)], and Cp*Ti(C3H3N2)(3) (4) were prepared in moderate yields by treating Cp*TiCl3 with the pyrazoles in the presence of Et3N or with their corresponding lithium salts in Et2O. The structures of 1 and 2 determined by X-ray crystallography indicate that these complexes fold a distorted tetrahedral geometry around Ti, and the pyrazolato ligands coordinate to Ti with eta(2)-N,N'-coordination mode. In contrast, one of the pyrazolato ligand in 4 coordinates to Ti with eta(1)-N-bonding, whereas the other two ligands were bound to Ti with eta(2)-N,N'-fashion. The Cp analogues, CpTiCl2(L) [L = C3H3N2 (5), 3,5-Me2C3HN2 (6), 3,5-(Pr2C3HN2)-Pr-i (7), and 3,5-Ph2C3HN2 (8)], were also prepared by the reaction of CpTiCl3 with the corresponding lithium salts in Et2O or n-hexane. The crystallographic analyses of 5 and 6 revealed that the pyrazolato ligands coordinate to Ti with eta(2)-N,N'-coordination mode. These complexes (1-3, 5-8) exhibited moderate catalytic activities for ethylene polymerization in the presence of methylaluminoxane (MAO), and the activities were highly affected by the substituent on the pyrazolato ligand employed. Complex 1 exhibited the highest activity affording polymer with uniform molecular weight distribution, suggesting that the polymerization proceeded with uniform catalytically active species. An increase in the steric bulk in the pyrazolato ligand led to a slight decrease in the activity by the Cp* analogues, whereas the activity by the Cp analogues increased upon increasing the steric bulk in the pyrazolato ligand employed.