Devolatilization of Mongolian coal (Baganuur coal (BC), Shievee Ovoo coal (SOC), and Shievee Ovoo dried coal (SOC-D)) was investigated by using bench-sized fixed-bed and rotary kiln-type reactors. Devolatilization was assessed by comparing the coal’s type and dry basis, temperature, gaseous flux, tar formation/generation, devolatilization rate, char yield, heating value, and the components of the raw coal and char. In the fixed bed reactor, higher temperatures increased the rate of devolatilization but decreased char production. BC showed higher rates of devolatilization and char yields than SOC or SOC-D. Each coal showed inversely proportional devolatilization and char yields, though the relation was not maintained between the different coal samples because of their different contents of inherent moisture, ash, fixed carbon, and volatile matter. Higher temperatures led to the formation of less tar, though with more diverse components that had higher boiling points. The coal gas produced from all three samples contained more hydrogen and less carbon dioxide at higher temperatures. Cracking by multiple functional groups, steam gasification of char or volatiles, and reforming of light hydrocarbon gas increased with increasing temperature, resulting in more hydrogen. The water gas shift (WGS) reaction decreased with increasing temperature, reducing the concentration of carbon dioxide. BC and SOC, with retained inherent moisture, produced substantially higher amounts of hydrogen at high temperature, indicating that hydrogen production occurred under high-temperature steam. The continuous supply of steam from coal in the rotary kiln reactor allowed further exploration of coal gas production. Coal gas mainly comprising syngas was generated at 700–800 °C under a steam atmosphere, with production greatest at 800 °C. These results suggest that clean char and high value-added syngas can be produced simultaneously through the devolatilization of coal at lower temperature at atmospheric pressure than the entrained-bed type gasification temperature of 1,300–1,600 °C.