The photocatalytic properties of Zn/Co zeolite imidazolate frameworks (ZIF-ZnCo) prepared by various Zn/Co ratio are of significantly diversity due to the morphology structure of the ZIF-ZnCo. Thereinto, the prepared ZIF-ZnCO-8:1 is excellent capability by virtue of its 3D cross-shaped structure. Spectral test results show that as-prepared novel 3D cross-shaped ZIF-ZnCo has a lower recombination rate of electron and hole pairs than the lamellar and dodecahedral, thus improving the photocatalytic ability. The photocatalytic ability of 3D cross-shaped ZIF-ZnCo was carefully investigated for removing mixed solution of Congo Red (CR) and Cr(VI). The photocatalytic reduction ability of 3D cross-shaped ZIF-ZnCo was 22% higher than ZIF-8 for Cr(VI). Meanwhile, CR was altogether removed at dark processing and Cr(VI) was removed 70% after dark processing 120min and photocatalytic 240min. Therefore, the high adsorption and photocatalytic capacity denote the potential application of 3D cross-shaped ZIF-ZnCo.