Bis(phenoxyimine)Zr complexes 1−8 containing a series of cycloalkyl groups on the imine-N's were synthesized (1: cyclopropyl; 2, 3: cyclobutyl; 4: cyclopentyl; 5, 7: cyclohexyl; 6, 8: 2-methylcyclohexyl). X-ray crystallographic analyses suggested that complexes 3, 5, and 8 assume an octahedral coordination geometry with a trans-phenoxy-O, cis-imine-N, and cis-Cl disposition and that the cycloalkyl groups on the imine-N's influence steric environments around the chlorine bound sites (i.e., potential polymerization sites). Upon activation with MAO at 25 °C, these complexes produced low-to-high molecular weight polyethylenes (PEs) (Mw 1900−960000, Mw/Mn 1.6−4.9) with very high efficiency (22−290 kg of PE/(mmol of cat. h)), which is comparable to or exceeds that seen with Cp2ZrCl2/MAO (28 kg of PE/(mmol of cat. h)). The cycloalkyl group has a profound effect on both catalytic activity and product molecular weight, indicating the critical importance of the substituent on the imine-N for polymerization cat...