In this paper, PHB, P(HO-co-HD), a various composition of P(HB-co-HV) copolymer and P(HB-co-HH) copolymer were studied both at normal temperature and in the process of increasing and decreasing temperature using FTIR spectroscopy technology. Results showed that FTIR spectra of PHAs with various compositions have distinguishing characteristics. Physical transformation occurred when PHAs were treated with heat denaturalization, and this physical process was reversible.