The development of Zn‐ion batteries (ZIBs) is always hindered by the ruleless interface reactions between the solid electrode and liquid electrolyte, and seeking appropriate electrolyte additives is considered as a valid approach to stabilize the electrode/electrolyte interphases for high‐performance ZIBs. Benefiting from the unique solubility of TiOSO4 in acidic solution, the composite electrolyte of 2 m ZnSO4+30 mm TiOSO4 (ZSO/TSO) is configured and its positive contribution to Zn//Zn cells, Zn//Cu cells, and Zn//NH4V4O10 batteries are comprehensively investigated by electrochemical tests and theoretical calculations. Based on the theoretical calculations, the introduction of TiOSO4 contributes to facilitating the desolvation kinetics of Zn2+ ions and guarantees the stable interface reactions of both zinc anode and NH4V4O10 cathode. As expected, Zn//Zn cells keep long‐term cycling behavior for 3750 h under the test condition of 1 mA cm−2–1 mAh cm−2, Zn//Cu cells deliver high Coulombic efficiency of 99.9% for 1000 cycles under the test condition of 5 mA cm−2–1 mAh cm−2, and Zn//NH4V4O10 batteries maintain reversible specific capacity of 193.8 mAh g−1 after 1700 cycles at 5 A g−1 in ZSO/TSO electrolyte. These satisfactory results manifest that TiOSO4 additive holds great potential to improve the performances of ZIBs.