The heat absorption, weight change and exhaust behavior of TiB2-based cermet powder mixtures with additions of WC, TiC and WC-TiC were analyzed by a simultaneous thermal analyzer coupled with a mass spectrometer (TG/DSC-QMS). Thermodilatometry was used to investigate the densification behavior due to sintering process of cermets. During the sintering process, the order of degassing is: water vapor, CO2 released by the reduction of adsorbed oxygen in the raw material powder, CO and CO2 released by the reduction of surface oxides of Co and Ni powder, WC powder, TiB2 and TiC powder. The addition of WC, TiC and WC-TiC accelerated the reduction of oxides on the surface of Co and Ni powders, and decreased the temperature point of liquid phase formation in TiB2-based cermet. WC and TiC dissolved in liquid CoNi binder and then precipitated on the undissolved TiB2 particles to form a typical core-rim structure during the sintering. This study is expected to lay a solid foundation for the development of high-performance TiB2-based cermets based on TiB2-CoNi, TiB2-WC-CoNi, TiB2-TiC-CoNi and TiB2-WC-TiC-CoNi cermets in the future.