Abstract TiN film is often coated on alumina rf windows to suppress multipactor due to high secondary electron emission (SEE) coefficients. In this paper, SEE coefficients of alumina ceramics and sapphire coated with TiN films of various thicknesses are investigated. The SEE coefficients were measured using a scanning electron microscope with a single-pulse electron beam (100 pA, 1 ms). The SEE coefficients of TiN-coated alumina ceramics were lower than those of uncoated ones and nearly unity for TiN thickness of more than 1 nm, even with incident energy of 1 keV. To emulate multipactor-induced surface heating, the SEE coefficients were also measured at high temperature. The results showed a decrease in the SEE coefficients with temperature for TiN thickness of more than 0.5 nm. TiN coating on an rf window should be as thin as possible, and 0.5–1 nm may be the optimum thickness for suppressing multipactor.