The urgent need for sustainable CO(2) conversion technologies has driven the development of advanced photocatalysts that harness solar energy. This study employs a CTAB-assisted solvothermal method to fabricate a Z-scheme heterojunction Fe-MOFs/V(O)-Bi(2)WO(6) (FM/V(O)-BWO) for photocatalytic CO(2) reduction. Positron annihilation lifetime spectroscopy (PALS) was employed to confirm the existence of oxygen vacancies, while spherical aberration-corrected transmission electron microscope (STEM) characterization verified the successful construction of heterointerfaces. X-ray absorption fine structure (XAFS) spectra confirmed that the defect configuration and heterostructure changed the surface chemical valence state. The optimized 1.0FM/V(O)-BWO composite demonstrated exceptional photocatalytic performance, achieving CO and CH(4) yields of 60.48 and 4.3 μmol/g, respectively, under visible-light 11.8- and 1.5-fold enhancements over pristine Bi(2)WO(6). The enhanced performance is attributed to oxygen vacancy-induced active sites facilitating CO₂ adsorption/activation. In situ molecular spectroscopy confirmed the formation of critical CO(2)-derived intermediates (COOH* and CHO*) through surface interactions involving four-coordinated and two-coordinated hydrogen-bonded water molecules. Furthermore, the accelerated interfacial charge transfer efficiency mediated by the Z-scheme heterojunction has been conclusively demonstrated. This work establishes a paradigm for defect-mediated heterojunction design, offering a sustainable route for solar fuel production.