Thin films of polyvinylidene (PVDF) and its copolymers containing 50 to 30 mole % of trifluoroethylene (TrFE) demonstrate rapid reversal of polarization under applied electric field, and can be used as ferroelectric materials in non-volatile memory devices. In this study, Fourier-transform infrared transmission (FTIR-TS) and grazing incident reflection absorption (FTIR-GIRAS) spectroscopy techniques were used to examine the changes in Curie transition temperature (Tc), chain and dipole orientation in selected VDF copolymer spun-cast films as a subjected to a reversible thermal-cycling treatment. A reversible solid-to-solid β-crystalline phase transition with thermal hysteresis and a favorable C-F dipole orientation along the electric field direction were observed for the sample subjected to thermal-cycling below its melting point (Tm). An irreversible β-crystalline phase transition with unfavorable C-F dipole orientation was observed for the sample treated to heating-cooling cycle above Tm. The results are reported in detail here.