The development of photoenzymatic non-natural reactions facilitates the synthesis of challenging high-value-added chiral compounds. However, this approach typically requires enzyme engineering to enhance both the catalytic activity and selectivity. Herein, we report a synergistic photoenymatic system comprising wild-type GluER and exogenous Ru(bpy)3Cl2·6H2O that enables the photoenzymatic enantioselective hydroalkylation of olefins. In this system, Ru(bpy)3Cl2·6H2O replaces protein engineering, driving an efficient catalytic cycle. The radical initiation was by electron transfer between excited Ru(bpy)3Cl2·6H2O and an in situ-formed ternary electron donor-acceptor (EDA) complex. This synergistic photo/biocatalytic system decreases the time-consuming and labor-intensive nature while providing an environmentally friendly methodology for chemical synthesis.