Abstract: The probe method for measuring the thermal conductivity of multifunction material hollow glassy microsphere is presented. Heating resistor and thermistor were embedded in a special probe. The temperature signal was processed in 8031 monochip microcomputer, and subsequently transferred to a 486PC. The thermal conductivity can be obtained by curve fitting calculation. The thermal conductivity of hollow glassy microsphere made in America and China had been measured. This method was proved to be accurate and easy,and can be used for measuring the thermal conductivity of powder materials and pyrotechnic compositions.