Carbon nanotubes (CNT) / polyvinylidene fluoride (PVDF) piezoelectric composite films for nanogenerator devices were fabricated by spray coating method. When the CNT/PVDF mixture solution passes through the spray nozzle with small diameter by the compressed nitrogen gas, electric charges are generated in the liquid by a triboelectric effect. Then randomly distributed ${eta}$ phase PVDF film could be re-oriented by the electric field resulting from the accumulated electrical charges, and might be resulted in extremely one-directionally aligned ${eta}$ phase PVDF film without additional electric field for poling. X-ray diffraction patterns were used to investigate crystal structure of the CNT/PVDF composite films. It was confirmed that they revealed extremely large portion of the ${eta}$ phase PVDF crystalline in the film. Therefore we could obtain the poled CNT/PVDF piezoelectric composite films by the spray coating method without additional poling process.