Catalytic syntheses of pyridine and its homologs by passing a mixed gas of acetylene, ammonia, and methanol over the catalyst of cadmium tungstate-Fuller's earth or cadmium chromate-Fuller's earth, were examined, from which the effect of reaction temperature, molar ratio of the gas mixture, space velocity, and concentration of the catalyst on the yield of pyridine was clarified. It was also found that pyridine is obtained by the use of acetaldehyde or crotonaldehyde in place of acetylene, with ammonia and methanol or formaldehyde, acrolein, or allyl alcohol in place of methanol, with acetylene and ammonia, under the same reaction conditions with the same catalyst.