Abstract Photocatalytic CO 2 reduction to valuable fuels is highly desirable to alleviate global warming and energy crisis. Herein, a stable aluminum‐porphyrin metal‐organic frameworks (MOFs) named Al−PMOF, with wide spectral response, is selected as platforms for the construction of efficient photocatalyst to convert CO 2 into CO. To enhance the activity of pristine Al−PMOF, highly active reaction sites are introduced through metallization of the porphyrin linkers with Cu 2+ . Furthermore, the polymerization of pyrrole in the channel of MOFs is also performed to improve the electron conductivity and narrow the band gap. The polypyrrole offers the conductive network to transfer the light‐generated electrons and thus enhances the efficient charge separation. The calculated electronic density of states based on the density functional theory (DFT) further prove the electron interaction between the polypyrrole and the MOFs, which benefit the enhancement of photocatalytic performance of Al−PMOF.