As a matrix resin of silica/epoxy hybrid encapsulation material with high heat resistance and low coefficient of thermal expansion, a tri-functional triglycidyl p-aminophenol (TGPAP) epoxy was successfully synthesized with the desired chemical structure by reacting epichlorohydrin with p-aminophenol using sodium hydroxide catalyst. In order to produce highly pure TGPAP with lower viscosity, a physical thin film vacuum distillation was carried out after synthesis, resulting in 97% purity with the viscosity of 700 cps at room temperature. Silica/TGPAP hybrid was fabricated using two kinds of ground fumed silica with different sizes of 20 μm and 9 μm. Glass transition temperature of the hybrid was found to be as high as 185 °C. Viscosity of the hybrid was 30,000 cps at room temperature before curing, implying good processability. When two different sizes of silica were used with 1 to 1 weight ratio, very low coefficient of thermal expansion of 22.79 ppm/°C was obtained. From thermal shock test, no cracks were observed even after 1,000 cycles of thermal shock between -40 °C and 125 °C when 67 wt% (45.8 vol%) of silica was involved in the hybrid. In conclusion, silica/TGPAP hybrid with improved processability, superior thermal shock resistance and low thermal expansion coefficient could be fabricated as electronic device encapsulation.