Bi2O3 modified ZSM-5 was prepared and used for synthesizing pyridine bases from ammonia and aldehydes. Bismuth was innovatively applied in the reaction of pyridine base synthesis. Photo-deposition method facilitated uniform dispersion of bismuth atomic clusters on the surface of ZSM-5. Bismuth atomic clusters were then oxidized to Bi2O3 nano-particles by O2 in the solution or air. The Lewis acid characteristics of Bi2O3 contributed to the formation of H+ during the reaction, and the properties of Bi2O3 facilitated the desorption of pyridine bases, therefore the prepared catalysts showed a better catalytic performance than the parent ZSM-5. The catalyst with 2.5 wt% bismuth had the best performance: the yield of pyridine bases was 1.8 times of that over parent ZSM-5, and the selectivity was as high as 91.0%. The catalyst also showed a good lifetime and regeneration performance.