In this paper, we propose a novel Fe-based polyoxometalates @ metal–organic framework (POM@MOF(Fe)) material synthesized by a one-step solvothermal strategy to combine the merits of adjustable structure of MOFs and excellent electrochemistry properties of POMs. Fe ions are connected by organic linkers 1,4-H2BDC and 4,4′-bipyridine to build frameworks and combined with Keggin-type H3PW12O40 units inside. A leaf-like structure of POM@MOF(Fe) crystals are obtained which exhibits good optical response in visible range with absorption edge at around 750 nm. Herein, we describe the assembly and characterization of a simplified solar cell based on POM@MOF(Fe) crystals modified the ZnO photoanode. The photovoltaic performance of solar cells with POM@MOF(Fe) modified the ZnO as photoanode without any sensitizer is enhanced compared to the bare ZnO which is clearly ascribed to the POM@MOF(Fe). The results demonstrate that this novel composite of POM@MOF(Fe) is a good electron–hole separation materials thus benefiting the photovoltaic property of ZnO. Hence, solar cells based on this novel photoanode can be expected to exhibit good photovoltaic performance.