It remains a grand challenge to probe the emissivity of calcium-magnesium-alumina-silicates (CMAS) at high temperatures. Herein, an innovative thermocouple-based infrared thermography (TBIT) method that combines a double hot thermocouple system and infrared (IR) camera is proposed to enable convenient measurement for CMAS emissivity at temperature >800 °C. To improve the measurement accuracy, a heat transfer model accounting for the possible uncertainty in temperature measurement is also developed to correct the real sample temperature on the hot thermocouple. On this basis, the feasibility of the TBIT method is verified by using the platinum-rhodium alloy as the benchmark. As a proof-of-principle demonstration, four different sets of CMAS samples, i.e., blast furnace (BF) slag are considered with their temperature-dependent emissivities characterized experimentally. It is found that the BF-like CMAS features an emissivity of 0.5–0.9 at 800–1500 °C. This research provides a fast, accurate and low-cost experiment effort to probe CMAS emissivity at high temperatures, which enriches the thermophysical properties of the CMAS materials.