The addition of tetrabasic lead sulfates (4BS) as additives to positive pastes will effectively address the shortcomings which occur during the usage of Lead-acid batteries, such as the premature capacity loss and the active substances shed in the positive paste. We synthesized 4BS seeds using the doped lead sulfate atmospheric hydrothermal method with the lead oxide, lead sulfate, and sulfuric acid as reactant. The purity and yield of 4BS reach above 99% and 92.5%, respectively, and the particle size was approximately 10 μm. The products have been characterized by scanning electron microscope and X-ray diffractometer. Composition analysis and processing method exploration of the effluent from the 4BS synthesis were finished as well.