The capacity to broaden the range of molecular weights displayed by polyolefinic materials is an important factor to be considered in the design of polymerization catalysts. Herein, the 2,6-dibenzhydryl-4-trifluoromethoxy modified bis(imino)pyridyl-ferrous chlorides, [2-[CMeN{2,6-{(C6H5)2CH}2-4-(F3CO)C6H2}]-6-(CMeNAr)C5H3N]FeCl2 [Ar = 2,6-Me2C6H3Fe1, 2,6-Et2C6H3Fe2, 2,6-i-Pr2C6H3Fe3, 2,4,6-Me3C6H2Fe4, 2,6-Et2-4-MeC6H2Fe5], are used as precatalysts in the solution polymerization of ethylene. On the activation with either MAO or MMAO, all complexes displayed high productivity [up to 18.4 × 106 g (PE) mol-1 (Fe) h-1 for Fe5/MAO], generating highly linear polyethylenes with a wide range of molecular weights (Mw range: 0.85 × 103 to 8.80 × 105 g mol-1). Notably, higher activity was achieved in hexane than in toluene under MAO activation, while the opposite trend was seen with MMAO, highlighting the key role played by solvent in the polymerization process. By comparison with structurally related iron catalysts, the presence of the electron withdrawing para-trifluoromethoxy group has the effect of increasing the molecular weight of the polyethylene. In addition to the polymerization studies, full synthetic and characterization details are presented for Fe1-Fe5 including the X-ray structures of Fe1 and Fe2.