The invention relates to a preparation method of an antimony pentoxide composite powder. The preparation method comprises the following steps: firstly, antimony trioxide is taken for refining; then the refined antimony trioxide dry powder is added into water, then creatinol-o-phosphate as a stabilizer and oxydol are added for oxidation reflux reaction, after the reaction, a reacting liquid is taken for dialysis for 2 to 3 times, redundant creation o-phosphate is removed, and an antimony pentoxide hydrosol is prepared; finally, the prepared antimony pentoxide hydrosol is added with zeolite powder, the mixture is stirred and then left to stand, precipitate is obtained through centrifugation, and the precipitate is filtered and dried so as to obtain the antimony pentoxide composite powder. The preparation method provided by the invention uses the creatinol-o-phosphate as the stabilizer, and the creatinol-o-phosphate contains a plurality of hydroxies and two inflaming retarding elements N and P, so that the stabilizing effect is good, the flame-retardant effect of the colloid of antimony pentoxide is improved, a zeolite powder is adopted for adsorbing the colloid of antimony pentoxide, so as to prepare the antimony pentoxide-zeolite powder composite powder, during the preparing process, the problem of much loss of antimony pentoxide dry powder during the drying process caused by relatively fine antimony pentoxide dry powder can be solved.