The heat capacity of poly(3-hydroxybutyrate) (P3HB) has been measured using a quantum design Physical Property Measurement System (PPMS), differential scanning calorimetry (DSC), and temperature-modulated differential scanning calorimetry (TMDSC) over the temperature range of (1.9 to 460) K. The results within the range of (1.9 to 250) K were obtained using the quantum design PPMS, and established the baseline of the solid heat capacity. This experimental low-temperature heat capacity was linked to the vibrational molecular motion of P3HB. The solid heat capacity of P3HB was computed based approximately on groups of vibration and skeletal vibration spectra. The skeletal vibration heat capacity contribution was estimated by a general Tarasov equation with three Debye characteristic temperatures Theta(1) = 549.1 K and Theta(2) = Theta(3) = 71.8 K, and ten skeletal modes, N-skeletal = 10. The experimental and calculated solid heat capacities agree with an error of +/- 0.2% over the temperature range from (5 to 250) K. The vibrational, solid heat capacity was extended to higher temperatures to judge additional contributions to the experimental heat capacity from other large-amplitude motion or latent heat during the quantitative thermal analysis of semi-crystalline P3HB. The liquid heat capacity of semi-crystalline P3HB above its melting temperature and of fully amorphous P3HB above the glass transition temperature was approximated by a linear regression and expressed as C-p(liquid)(exp)= 0.1791 T + 94.722 in units of J.K (1).mol (1). The calculated solid and liquid heat capacities can serve as equilibrium baselines for the quantitative thermal analysis of semi-crystalline P3HB. Also, the integral thermodynamic functions of enthalpy, entropy and free enthalpy for the equilibrium condition were calculated using estimated parameters of transitions. (C) 2013 Elsevier Ltd. All rights reserved.