Polyolefin elastomer (POE) has emerged as a promising encapsulant for photovoltaic modules, attributed to its exceptional water vapor barrier properties, robust weather resistance, and enhanced anti-potential induced degradation (anti-PID) capabilities. Despite these advantages, the interfacial adhesion of POE remains a significant challenge, particularly its suboptimal bonding with glass and solar cells, which impedes its broader application within the photovoltaic industry. This study introduced glycidyl methacrylate (GMA) monomers into POE through a photo-induced iron-catalyzed alkylation reaction, developing a novel polyolefin encapsulant for photovoltaic modules. The encapsulant was designed to possess high light transmittance, enhanced adhesion, and elevated resistivity. The modified POE boasts an impressive light transmittance nearing 98% and an adhesive strength of 28.3 N cm−1, both superior to traditional ethylene-vinyl acetate copolymer (EVA) materials. Additionally, this work delves into the correlation between crystallization behavior and light transmittance, elucidating the influence of GMA incorporation on the adhesion and insulation properties of POE through gaussian simulations.