The radius heating by Joule effect and cooling compensation of PeItier effect are used together to set up a device and a method to determine the thermal conductivity,λ, and diffusivity,a,of energetic material by means of microcalorimetry, The λand a values of 10 materials,including four standards(PTFE, PMMA, quartz glass,high density polyethylene)and six polymer bonded explosives(JH-9105, JOB-9003,JO-9159 , JO-9185, JB-9001 and JOB-9006),were determined at 298. 2K. The experimental data analysis shows that the deviations of λ and a of 4 standard substances are less than 0.8% and 0.4% respectively compared with those in the known references. The relative standard deviation of determining unequilibrium heat and radius flux are correspondingly higher than 0.4% and 0.1%.The overall relative standard deviations of determined λ and a are within the range of 1.2%.The determination errors of the unequilibrium heat and the internal and external radii of the cylinder sample are the major factors affecting the accuracy of determining the λ and a.