The structural, ferroelectric, and piezoelectric properties of poly (vinylidene fluoride–trifluoroethylene)[P (VDF–TrFE)] gels fabricated using poly (pyridinium-1, 4-diyliminocarbonyl-1, 4-phenylenemethylene thiocyanate)(PICPM-SCN) as a gelator are investigated in this study. The P (VDF–TrFE)/PICPM-SCN composites formed thermally reversible physical gels and their analysis by Fourier transform infrared spectroscopy revealed that the P (VDF–TrFE) molecules in these gels exhibit predominantly the ferroelectric phase I (Form β). Furthermore, the polarization switching peaks of the P (VDF–TrFE)/PICPM-SCN gel films were clearly observed. The coercive electric field for these gel films was estimated to be 2 MV/m, which is dramatically lower than the values typically observed for P (VDF–TrFE) solid films (50 MV/m). Finally, the P (VDF–TrFE)/PICPM-SCN gel films exhibited a piezoelectric response, and the highest piezoelectric coefficient was determined to be∼ 53 pm/V at an applied voltage frequency of 4 kHz.