Thermochromic phase change composites (TPC) exhibit versatile functions under electrothermal stimuli, which are extensively applied as packaging, insulation and circuit components in considerable advanced smart electronics. However, space charge accumulation under DC voltages is still a critical and universal issue for the serious deterioration of functionalities and life-span of TPC and electronics. This study presents a novel strategy of suppressing space charge in thermochromic phase change epoxy composites (TPCE) by constructing interfacial barrier from tribo-positive shell thermochromic phase change microcapsules. The strong tribo-positive melamine-formaldehyde (MF) shell of microcapsules can establish negative charge barriers in the interfaces between microcapsules and epoxy matrix through triboelectrification, which is directly verified by Kelvin probe force microscopy. Pulsed electroacoustic measurement results exhibit the space charge accumulation in TPCE under an extreme electric field strength of 50 kV/mm and an elevated temperature of 70 °C can be significantly diminished by 39.3% compared to that of neat epoxy resin after incorporating merely 1 phr MF shell microcapsules, affirming the effect of interfacial barrier on space charge inhibition. The interfacial barrier could improve the charge carrier dissipation and mitigating the space charge accumulation as confirmed by hopping conduction analysis. Moreover, DC breakdown strength of TPCE can also be enhanced by 12.3% and 6.1% with 1phr microcapsules at 30 °C and 70 °C compared to that of neat epoxy resin owing to the suppressed space charge. The results provide a potential approach of designing high-performance thermochromic phase change composites for smart electrical and electronic devices.