The effects of SnSO4 as an electrolyte additive on the microstructure of positive plate and electrochemical performance of lead acid battery made from a novel leady oxide are investigated. The novel leady oxide is synthesized through leaching of spent lead paste in citric acid solution. The novel leady oxides are used to prepare working electrode (WE) subjected to electrochemical cyclic voltammetry (CV) tests. Moreover, the novel leady oxides are used as active materials of positive plate assembled as a testing battery of 1.85 A h capacity. In CV tests, SEM/EDX results show that the major crystalline phase of the paste in WE after CV cycles is PbSO4. The larger column-shaped PbSO4 crystals easily generate in the paste of WE without an electrolyte additive of SnSO4. However, PbSO4 crystals significantly become smaller with the addition of SnSO4 in the electrolyte. In batteries testing, SEM results show that an electrolyte additive of SnSO4 could effectively decrease PbO2 particle size in the positive active materials of the teardown battery at the end of charging procedure. It is indicated that an electrolyte additive of SnSO4 could have a positive influence on restraining larger particles of irreversible sulfation in charge/discharge cycles of battery testing.