6-Benzimidazolylpyridyl-2-carboximidic half-titanocene complexes, Cp′TiLCl (Cp′ = C5H5, MeC5H4, C5Me5, L = 6-benzimidazolylpyridine-2-carboxylimidic, C1–C13), were synthesized and characterized along with single-crystal X-ray diffraction. The half-titanocene chlorides containing substituted cyclopentadienyl groups, especially pentamethylcyclopentadienyl groups were more stable, while those without substituents on the cyclopentadienyl groups were easily transformed into their dimeric oxo-bridged complexes, (CpTiL)2O (C14 and C15). In the presence of excessive amounts of methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all half-titanocene complexes showed high catalytic activities for ethylene polymerization. The substituents on the Cp groups affected the catalytic behaviors of the complexes significantly, with less substituents favoring increased activities and higher molecular weights of the resultant polyethylenes. Effects of reaction conditions on catalytic behaviors were systematically investigated with catalytic systems of mononuclear C1 and dimeric C14. With C1/MAO, large MAO amount significantly increases the catalytic activity, while the temperature only has a slight effect on the productivity. In the case of C14/MAO catalytic system, temperature above 60 °C and Al/Ti value higher than 5000 were necessary to observe good catalytic activities. In both systems, higher reaction temperature and low cocatalyst amount gave the polyethylenes with higher molecular weights. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3396–3410, 2008