Lead–acid battery performance is severely limited to negative plate sulfation (irreversible formation of lead sulfate).The influence of surfactants types in lead-acid battery electrolyte has been investigated on the sulfation of negative active material (NAM) under high-rate partial-state-of-charge (HRPSoC) opreation. However, it is still an open investigation to explore that how to make the lead sulfate crystals more electrochemically active and how surfactants affect on their pattern growth. This research demonstrates that various surfactants have different effects on NAM sulfation using XRD (X-ray diffraction), SEM (scanning electron microscopy), CV (cyclic voltammetry) and EIS (electrochemical impedance spectroscopy) techniques, which in some cases their behaviors are conversely. Amongst all tested surfactants, the cell with anionic sodium dodecyl sulfate surfactant (SDS) exhibits the longest cycle life with the least overcharge and fine PbSO4 crystals. The cell with cationic cethyl trimethyl ammonium bromide (CTAB) surfactant shows opposite effects.