Abstract: The present disclosure discloses a preparation method of an organosilica/ceramic composite membrane with a gradient pore structure. The preparation method comprises: (1) selecting a porous ceramic material as a membrane support layer; (2) gradually replacing a solvent with water to prepare zirconium colloidal sols with different particle sizes, and successively coating the prepared zirconium colloidal sols onto a ceramic support from large to small so as to form a membrane transition layer with a gradient pore structure; and (3) catalytically synthesizing an organosilica polymeric sol using hydrochloric acid, coating the prepared organosilica sol onto the preheated transition layer through ultrasonic thermal spraying to undergo heat treatment, so as to prepare the organosilica/ceramic composite membrane with the gradient pore structure. According to the present disclosure, the transition layer with the gradient pore structure is prepared by using the zirconium colloidal sols with different particle sizes.