Phase transition properties of the copolymer films of polyvinylidene fluoride (PVDF) and trifluoroethylene(TrFE), P(VDF-TrFE), were studied with X-ray diffraction (XRD) and polarization modulated ellipsometry (PME). XRD studies on both Langmuir-Blodgett (LB) films and spin coated films exhibit conversions from ferroelectric phase to paraelectric phase at $108{pm}2^{circ}C$ on heating and paraelectric phase to ferroelectric phase at $78{pm}2^{circ}C$ on cooling. The presence of the ferroelectric-paraelectric phase transition is also confirmed by the PME technique for the first time in this study. PME was proved to be a very sensitive tool in the measurement of the structural changes at the nano-thickness films.