The invention discloses a method for synthesizing tetrabasic lead sulfate by utilizing positive electrode waste lead plaster and application thereof. The method comprises the following steps of washing, filtering, separating, dehydrating, drying, sieving and purifying the positive electrode waste lead plaster, and then, carrying out chemical analysis on a treated mixture, thereby obtaining contents of various components of lead sulfate, lead oxide and free lead in the treated mixture according to chemical analysis, adding lead powder to carry out mixing, grinding and sieving, so that the molar ratio of the lead oxide to lead sulfate after hybrid reaction is (4-5):1; and preserving the heat and presintering the sieved mixture in a resistance furnace, and then heating up to sinter, cooling and drying to obtain the tetrabasic lead sulfate. The method can be used for a storage battery manufacturer to prepare according to convenient conditions of the manufacturer, is simple and easy to implement; the prepared tetrabasic lead sulfate can completely satisfy performance requirements while being applied to battery production, so that early capacity loss of a lead storage battery is restrained, various electrical performances of the battery and a cycle life of the storage battery are greatly improved and prolonged, respectively, thereby not only solving a treatment problem of lead-containing waste materials of the storage battery enterprises, but also lowering production cost of enterprises and changing waste into things of value.