A method and apparatus for measuring the thermal conductivity of materials using modulated differential scanning calorimetry (MDSC). Two MDSC heat capacity measurements are made consecutively. One measurement is made under conditions which ensure obtaining a fairly accurate value for the heat capacity of the material ("quasi-ideal conditions"). Another measurement is made under conditions such that the measured effective heat capacity differs from the accurate value of the heat capacity due to thermal conductivity effects. Generally, the non-ideal conditions differ from the ideal conditions by one parameter, such as the size of the sample, the modulation frequency used to measure the heat capacity, or, for thin films, the presence or absence of a specimen on the thin film. The thermal conductivity of the material is then calculated from the difference between the heat capacity measured under quasi-ideal conditions and the effective heat capacity measured under non-ideal conditions.