The migration behavior of the alkali metals and chlorine were studied during rice straw and corn straw gasification in a fixed bed reactor at various temperatures using thermodynamic equilibrium calculations, X-ray diffraction (XRD), and scanning electron microscopy/energy dispersive spectrometry (SEM-EDS). The results showed that K and Na were released mostly in chloride form. The release of potassium, sodium, and chlorine increased upon the increase in temperature from 600 to 1000 °C. The maximum amounts of potassium, sodium, and chlorine that were released from rice straw were 38.9%, 18.7%, and 34.9%, respectively. The maximum amounts of potassium and chlorine that were released from corn straw were 24% and 43.6%, respectively, which occurred at 1000 °C. The maximum amount of sodium released from corn straw was 77.6%, at 700 °C, and the amount of sodium released was greater than that of potassium. Most of the potassium and sodium was converted into insoluble carbonate, sulfate, silicate, and aluminosilicate compounds in the gasification ash.