a composite catalytic membrane applied to catalytic esterification and preparation method thereof are provided . the composite catalytic membrane is porous , and includes nonwoven fabric as base membrane and catalytic coating which is formed on the surface of nonwoven fabric and in the pores and gaps between the nonwoven fabric fibers . the catalytic coating uses solid acid as catalyst and polymer or modified sulfonated polymer as membrane - forming material . the membrane is formed by coating or immersion method , and the composite catalytic membrane is obtained by cross - linking after forming . the greenization and high efficiency of catalytic esterification and preparation of biodiesel can be achieved owing to the microporous structure and huge specific surface area of the composite catalytic membrane . the composite catalytic membrane has high mechanical strength , good reproducibility and stability and easily enables continuous repetitive production of catalytic esterification . the process is simple and easy to control and scale - up .