The specific heat capacity (C sp ) of polyvinyl alcohol (PVOH) blends with cassava starch (CSS) was studied by the differential scanning calorimetry method. Specimens of PVOH-CSS blends: PPV37 (70 mass% CSS) and PPV46 (60 mass% CSS) were prepared by a melt blending method with glycerol added as a plasticizer. The results showed that the specific heat capacity of PPV37 and PPV46 at temperatures from 330 K to 530 K increased from (2.963 to 14.995) J · g −1 · K −1 and (2.517 to 14.727) J · g −1 · K −1 , respectively. The specific heat capacity of PVOH-CSS depends on the amount of starch. The specific heat capacity of the specimens can be approximated by polynomial equations with a curve fitting regression >0.992. For instance, the specific heat capacity (in J · g −1 · K −1 ) of PPV37 can be expressed by C sp = −17.824 + 0.063T and PPV46 by C sp = −18.047 + 0.061T , where T is the temperature (in K).