Abstract: Layered double hydroxide (LDH) with special layered structure has been proved to have excellent hole transport capacity and good stability. Herein, we report a high efficient composite photocatalyst of CoAl-LDH and BiPO4 prepared by hydrothermal and chemical adsorption (denoted as CoAl-LDH/BiPO4). Phenol can be entirely degraded by 1% CoAl-LDH/BiPO4 under 30 min ultraviolet (UV) light irradiation, and the degradation rate constants k are 3 times and 39 times higher than that of pure BiPO4 and CoAl-LDH, respectively. The enhanced photocatalytic activity can be attributed to effective holes transfer from BiPO4 to CoAl-LDH, which hinders the recombination of photogenerated charge carriers. In addition, the combination of BiPO4 and CoAl-LDH avoids the agglomeration of BiPO4 and improves the stability of BiPO4. Active species capture experiments indicate that superoxide radicals (·O2−) are the main active species responsible for the degradation of phenol. This work provides technical approaches and research ideas for solving the photogenerated charge carrier recombination problem of photocatalyst.