In this work, a series of oxovanadium complexes bearing the ligands (S,E)-(+)-2, 6-dialkyl-N-(2-((2-(4-isopropyl-4,5-dihydrooxazole-2-yl)phenyl)amino)benzylidene)aniline (dialkyl = dimethyl (V1), diethyl (V2), and isopropyl (V3)) have been synthesized and characterized by FTIR spectroscopy and elemental analysis. Moreover, the molecular structures of complexes V2 and V3 were defined by X-ray diffraction. On activation with ethylaluminium sesquichloride (Al2Et3Cl3), these complexes exhibited high activity towards ethylene polymerization (up to 1.39 × 107 g molv-1 h-1) and showed excellent thermal stability (up to 60 °C). The obtained polyethylene had a moderate molecular weight (21.9 × 104 to 66.4 × 104 g mol-1) and exhibited narrow distribution (1.91 to 2.86) and unimodal features. The effect of the substituents on the ligands was also investigated in detail. The compound bearing the diisopropyl group showed the highest activity toward ethylene polymerization as the bimolecular deactivation of the catalyst can be effectively inhibited by the steric hindrance of the ortho-substituent on aniline. The complex V2 with moderate steric hindrance was also evaluated as a catalyst for the copolymerization of ethylene with norbornene and showed moderate to high activity.