Organic-inorganic hybrid microcapsules encapsulating 2-phenylimidazole (2-PhIm) were prepared byPickering emulsion polymerization of styrene and divinyl benzene using methacryloyloxy silanemodifiedsilica particles as the stabilizer, and served as a thermal latent curing accelerator fordiglycidylether of bisphenol A epoxy/anhydride system. The one-component curing compositioncontaining 5 wt% of the microcapsules exhibited an excellent storage stability. The pot life at roomtemperature was as long as 30 days, while which of 2-PhIm curing system was only 2 days. At elevatedtemperature, the encapsulated 2-PhIm could be released from microcapsules effectively, and instantlyaccelerated the curing reaction. Meanwhile, the addition of microcapsules did not cause an adverse effecton the thermomechanical performance of the epoxy thermosets. In addition, the latency and curingbehavior could be facilely regulated at a wide range of temperature by adjusting monomer ratios of thepolymer matrix, to match different process temperatures. The microcapsules with robust cross-linkedpolystyrene matrix structure also showed good resistance to shearing forces, indicating their feasibilityfor high-speed mixing or kneading process in practical applications. It is suggested that the novel latentcuring accelerator is potential for high-performance one-pot epoxy formulations, particularlyrecommended for application in electronic packagingfields.