In order to explore the influence of different preparation methods on the morphologies, structures and surface species of cerium-manganese solid solutions, as well as clarify the relationship between the structures and their catalytic performances, four kinds of cerium-manganese solid solutions〔containing 15% manganese in theory, n(Ce)∶n(Mn)=0.85∶0.15〕were prepared by the nano-casting method, hydrothermal method, co-precipitation method and thermal decomposition method, respectively. The physical and chemical properties of the catalysts were characterized by XRD, FESEM, TEM, N2 adsorption-desorption, ICP-OES and XPS. The catalytic performances of catalysts were evaluated by the selective catalytic synthesis of N-benzylideneaniline from benzyl alcohol and aniline under air atmosphere. The results showed that the catalyst prepared by nano-casting method possessed the best catalytic activity with highest aniline conversion of 67.9%, N-benzylideneaniline selectivity of 99.4% and time space yield of 0.56 mmol/(gcat·h). Compared with the other three preparation methods, the best performance of cerium-manganese solid solution prepared by nano-casting method could be attributed to its larger surface area, specific mesoporous structure and richer content of surface Ce3+ and Mn3+.