The heat capacity of poly(vinyl methyl ether) (PVME) has been measured using adiabatic calorimetry and temperature-modulated differential scanning calorimetry (TMDSC). The heat capacity of the solid and liquid states of amorphous PVME is reported from 5 to 360 K. The amorphous PVME has a glass transition at 248 K (-25 degrees C). Below the glass transition, the low-temperature, experimental heat capacity of solid PVME is linked to the vibrational molecular motion. It can be approximated by a group vibration spectrum and a skeletal vibration spectrum. The skeletal vibrations were described by a general Tarasov equation with three Debye temperatures Theta(1) = 647 K, Theta(2) = Theta(3) = 70 K, and nine skeletal modes. The calculated and experimental heat capacities agree to better than +/- 1.8% in the temperature range from 5 to 200 K. The experimental heat capacity of the liquid rubbery state of PVME is represented by C-p(liquid) = 72.36 + 0.136 T in J K-1 mol(-1) and compared to estimated results from contributions of the same constituent groups of other polymers using the Advanced Thermal AnalysiS (ATHAS) Data Bank. The calculated solid and liquid heat capacities serve as baselines for the quantitative thermal analysis of amorphous PVME with different thermal histories. Also, knowing C-p of the solid and liquid, the integral thermodynamic functions of enthalpy, entropy, and free enthalpy of glassy and amorphous PVME are calculated with help of estimated parameters for the crystal. (c) 2005 Wiley Periodicals, Inc.