Poly(propylene oxide) (PPO), a novel soft elastomeric material, and its composites were investigated as a new dielectric electroactive polymer (EAP). The PPO networks were obtained from thiol-ene chemistry by photochemical crosslinking of ,!-diallyl PPO with a tetra-functional thiol. The elastomer was reinforced with hexamethylenedisilazane treated fumed silica to improve the mechanical properties of PPO. The mechanical properties of PPO and composites thereof were investigated by shear rheology and stress–strain measurements. It was found that incorporation of silica particles improved the stability of the otherwise mechanically weak pure PPO network. Dielectric spectroscopy revealed high relative dielectric permittivity of PPO at 103 Hz of 5.6. The relative permittivity was decreased slightly upon addition of fillers, but remained higher than the commonly used acrylic EAP material VHB4910. The electromechanical actuation performance of both PPO and its composites showed properties as good as VHB4910 and a lower viscous loss.