Copper tetra-amine phthalocyanine (NH 2 -CuPc) was grafted onto barium titanate (BaTiO 3 ) whose surface was modified by carboxylic polyarylene ether nitrile (CPEN) to afford a nano-filler (CPEN-f-BaTiO 3 @NH 2 -CuPc). Through a solution-casting method combined with ultrasonic dispersion technology, the obtained CPEN-f-BaTiO 3 @NH 2 -CuPc was successfully incorporated into biphenyl polyarylene ether nitrile (BP-PEN) matrix to prepare nanocomposite films with various mass fractions of CPEN-f-BaTiO 3 @NH 2 - CuPc (0, 2.0, 5.0, 10.0 and 20.0 wt%). After that, the nanocomposite films were unidirectionally stretched with various stretching ratios at 280 ∘ C. All the nanocomposite films show excellent mechanical and thermal stability, which is provided by the BP-PEN matrix. The crystallinity and mechanical, thermal and dielectric properties of the nanocomposite films are efficiently enhanced after the unidirectional hot-stretching process. The results show that hot-stretching is a useful method for improving the mechanical and crystallization behaviors as well as the thermal and dielectric properties of the nanocomposite films.