The improvement of mechanical properties and toughness of nanoparticles for epoxy composites was mostly dependent on the disperse state of nanoparticles in epoxy matrices. When the content of nanoparticles was higher than a threshold value, it was easy to aggregate and then affect the improvement effect. Pickering emulsion was prepared using SiO2 nanoparticles as emulsifier and functional monomer as oil phase. The influence of Pickering emulsion on the curing process was investigated. The effect of Pickering emulsion on the mechanical properties, toughness, and glass transition temperature (Tg) was studied. Impact and tensile fracture surface were observed by scanning electron microscopy (SEM). Results from differential scanning calorimeter (DSC), tensile, impact, and fracture toughness tests are provided. The results indicated that the introduction of Pickering emulsion can eliminate the residual stress and accelerate curing reaction. Epoxy composites were capable of increasing tensile strength by up to 29.9%, impact strength of three‐fold, fracture toughness of 35%, and Tg of 20.7°C in comparison with the reference sample. SEM images showed that SiO2 nanoparticles exhibit a good dispersion in epoxy matrix. The increases in mechanical properties, toughness, and Tg of epoxy composites were attributed to the “Second Phase Toughness” mechanism.