The invention discloses an electrolytic manganese residue-based micro-mesoporous ZSM-5 catalyst and a preparation method, wherein the catalyst is represented by the following general formula (1) CeO2/Mn-H-ZSM-5, Mn-H-ZSM-5 is a carrier, H-ZSM-5 is micro-mesoporous ZSM-5, Mn is a manganese element, and the preparation method of the molecular sieve mainly adopts solid waste electrolytic manganese residue as a main material, does not extraction of Si and Al, and comprises: carrying out mixing roasting on the electrolytic manganese residue and sodium hydroxide, adding a certain amount of tetrapropylammonium hydroxide (TPAOH), cerous nitrate and a poly(diallyldimethylammonium chloride) (PDADMAC) solution, carrying out one-step hydrothermal synthesis, filtering, washing, drying, and roasting toobtain the molecular sieve. According to the present invention, the CeO2/Mn-H-ZSM-5 has a specific surface area of 325-458 m<2>/g, a mesopore volume of 0.067-0.550 cm<3>/g, a mesopore size of 2-16 nm,and an average pore size of 2.25-5.58 nm; and the molecular sieve has adjustable pore size, can improve the utilization value of electrolytic manganese residue, and has good activity and good stability in catalyzing oil fume VOCs.