Organic P(VDF-TrFE) 70/30 copolymer thin films were fabricated on Pt/Ti/SiO2/Si(1 1 1) and ITO/glass substrates at 140 °C using a spin coater. Both P(VDF-TrFE) thin films exhibited ferroelectric β-phase crystallinity, as confirmed by X-ray diffraction analysis. The polarization–electric hysteresis loops of the P(VDF-TrFE) thin films on the Pt and indium-tin-oxide substrates showed high remnant polarizations of 15.5 and 11.8 μC/cm2, respectively. Atomic force microscopy characterization showed rod-like features of the P(VDF-TrFE) thin films on both substrates, where larger rod diameters were observed on the Pt substrate compared to those fabricated on the ITO substrate. Piezoelectric force microscopy measurements further confirmed the superior piezoelectric and ferroelectric properties of the P(VDF-TrFE) thin films on the Pt substrate compared to those on the ITO substrate, which arose from the increased diameter of the rod-like features.