The invention relates to a separation method of a PbO, PbSO4 and PbO2 mixture, in particular to a process and a technology of resource comprehensive utilization of a lead containing material of a waste lead storage battery, and belongs to the technical field of comprehensive utilization of three wastes of the waste lead storage battery or separation and refining of inorganic compounds. The separation method comprises steps as follows: PbO, PbSO4 and PbO2 mixture containing lead plaster obtained from the lead containing material, treated with a physical separation method, of the waste lead storage battery is taken as a raw material, the raw material is treated with technologies including acid pickling dissolving, leaching dissolving, separation, refining and solid-liquid separation coupling, and separation of the PbO, PbSO4 and PbO2 mixture is realized. The process is reasonable, the preparation method is simple, the purity and the yield of products are high, by-products in the process are greatly reduced, the comprehensive utilization cost of the lead plaster resource is reduced, the process is safe and reliable, and large-scale industrialization is facilitated.