To comprehensively understand the release characteristics of alkali metals which can cause corrosion and slagging problems in municipal solid waste (MSW) incinerators, the temporal concentrations of sodium (Na) and potassium (K) in a 16 MW MSW incinerator were measured employing a calibrated flame emission spectroscopy (FES) system. The experimental results revealed that the concentrations of alkali metals increased first and then decreased from the left side to the right side of the MSW incinerator. The maximum concentrations of Na and K were 111 ppm and 184 ppm, respectively. The peak and average concentrations of K near the left wall were 27 % and 58 % higher than those near the right wall at the same height of the MSW incinerator, owing to the different combustion stages of the MSW. The differences of the peak and average concentrations of K at the different heights of the MSW incinerator were 33.7 % and 23.5 %, respectively. Moreover, a positive correlation between the concentration of alkali metals and flame temperature was confirmed during the char phase combustion stage. Since the primary air distribution pattern of MSW incinerator decreased form the left side to the right side, the concentration of alkali metals near the left wall was positively correlated with the primary air flow, and that near the right wall exhibited a positive correlation with the garbage caloric value. This research provided an effectual solution for in-situ measurement of alkali metal concentration and flame temperature in MSW incinerators.