The structure and ferroelectric phase transition behavior were investigated for heat-treated samples of vinylidene fluoride-trifluoroethylene (VDF-TrFE) copolymers with 73 and 65% VDF molar contents. The temperature of the transition from the ferroelectric to the paraelectric phases increased when the samples were annealed in the temperature region of the above phase transition. The domain size, evaluated from the integrated width of the X-ray reflections, also increased drastically at these annealing temperatures. As the annealing temperature increased above the transition point, the resulting sample showed a reduction of the transition temperature. In this case, the domain size decreased slightly and the trans sequential length in the crystalline domain decreased, corresponding to structural disorder due to the invasion of gauche bonds into the trans zigzag chains. In the case of the 65% VDF sample, annealing in the phase transition temperature region resulted in a tilting phenomenon of chains in the crystalline region, but this phenomenon was not detected for the 73% VDF sample.