AbstractFlexible high‐temperature polymeric dielectrics with advanced dielectric properties are urgently demanded in various applications. In this work, series of polymer blend films were prepared from aromatic polythiourea (ArPTU) and polyimide (PI). The experimental results revealed that the blend films were properly engineered to achieve higher breakdown strength, greater dielectric constant, and larger energy density than pure PI film. For instance, the optimum property was obtained from the blend film with 10 wt% ArPTU, exhibiting prominent dielectric properties (K = 4.52, Eb = 443 MV/m), enhanced energy density (4.00 J/cm3) as well as excellent heat resistance (Tg = 419°C). In addition, stable dielectric properties at broad temperature range from −50 to 250°C were also acquired. It is deduced that the good compatibility from ArPTU and PI with similar polarity are responsible for the improved properties. The superior comprehensive properties which combine the advantages of ArPTU and PI suggest the potential applications of ArPTU/PI blend film in high‐temperature dielectric areas.