Mesoporous C@ZnO hollow spheres were successfully synthesized through a carbon-sphere template combined hydrothermal method. The photocatalytic activities of the samples to rhodamine B (RhB) were investigated, and the sample of 3 wt% carbon has the best photocatalytic activity to RhB. The excellent photocatalytic performance could come from both enhanced photogenerated electron–hole pair separation, and the larger specific surface area induced by mesoporous hollow nanostructure. The photocatalytic performance sensitively depends upon content of amorphous carbon. Too much or too little carbon content decreases sample performance. The changes in performance according to carbon content are probably a result of the competing mechanism: the increasing rate of separation efficiency of photogenerated carriers and the decreasing contact area of ZnO with RhB according to the carbon content. This work would help us to better understand the important roles of carbon content in the fabricated nano-heterojunctions and also provide us with a feasible route to improve UV photocatalytic activities of ZnO and other metal oxides greatly.