Polysiloxane-based gel electrolyte (PBGE) is prepared and investigated as a new gel electrolyte for valve-regulated lead-acid (VRLA) batteries. PBGE particles, characterized by means of Fourier transform infrared (FTIR) spectroscopy, cyclic voltammetry (CV) and scanning electron microscopy (SEM), reveal good stability and their particle sizes are 30–50nm. The initial cyclic properties of the absorptive glass mat (AGM)–PBGE and AGM–colloid silica gel electrolyte (CSGE) hybrid batteries are investigated by electrochemical techniques, scanning electron microscopy and X-ray diffraction (XRD). The addition of PBGE improves the utilization efficiency of positive active material (PAM) in AGM–PBGE hybrid batteries and thus enhances the batteries capacity compared with the AGM–CSGE reference batteries. Cyclic overdischarge tests show that the AGM–PBGE hybrid batteries have superior recharge and discharge during partial-state-of-charge (PSoC). It is also found that the greatly enhanced electrochemical performance of the AGM–PBGE batteries may be due to higher charge efficiency, good conductivity with lower internal resistance and the open three-dimensional network structure of the polyelectrolyte. The analysis results of SEM and XRD indicate that softening and shedding of positive active material are the main causes of failure for the two hybrid batteries.