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A co-crystallized zeolite catalyst for synthesizing pyridine bases comprises (by weight) : from 25% to 45% of rare earth-ZSM5/ZSM11 co-crystallized zeolite, from 0.5% to 3.0% of TiO2, and the balance being alumina and kaolin. The catalyst can be prepared by mixing rare earth-ZSM5/ZSM11 co-crystallized zeolite, TiO2, alumina, kaolin, and water homogeneously, wherein the weight ratio of solid to water in the mixture is in the range from 0.2 to 0.5, spray shaping and then drying. The process for synthesizing pyridine bases in presence of such catalyst can be easily operated and has good pyridine bases selectivity.