A novel polymerization mechanism transformation strategy, combining ring-opening metathesis polymerization (ROMP) and visible light induced cationic polymerization, is successfully applied for the synthesis of polyethylene-graft-poly(cyclohexene oxide) (PE-g-PCHO). First, cis-cyclooctene (COE) was polymerized via ROMP in the presence of a chain transfer agent and quantitatively hydrobrominated to give bromo functional polyethylene (PE-Br). Subsequent irradiation of PE-Br in the visible range using dimanganese decacarbonyl (Mn-2(CO)(10)) and diphenyl iodonium hexafluorophosphate (Ph2I+PF6) as radical generator and oxidant, respectively, initiated cationic polymerization of cyclohexene oxide (CHO) resulting in the formation of PE-g-PCHO. The effect of irradiation time and Mn-2(CO)(10) concentration on the grafting density and efficiency was evaluated. Both the precursor polymers and the corresponding graft copolymers were characterized by H-1 NMR and Fourier transform infrared (FT-IR) spectroscopy, gel-permeation chromatography (GPC), and differential scanning calorimetric (DSC) analyses.