Copper tetra-amine phthalocyanine (NH₂-CuPc) was grafted onto barium titanate (BaTiO₃) whose surface was modified by carboxyl-functionalized polyarylene ether nitrile (CPEN), (CPEN-f-BT@CuPc), using rotary coating technology combined with an ultrasonic dispersion technology and a post-treatment bonding process. The CPEN-f-BT@CuPc/polyarylene ether nitrile (PEN) nanocomposites show stable dielectric constant and energy density in the temperature range of 25–160 °C, which demonstrate huge potential for use as organic film capacitors.