Steam gasification of the HyperCoals (ash-free coal extracts) with the physical addition of 5.8%-6.0% K2CO3 was conducted at 1023 K on a thermogravimetric apparatus that was equipped with an on-line quadrupole mass spectrometer. The catalytic gasification of the HyperCoals demonstrated a much higher gasification rate than the catalytic gasification of the raw coals, Interactions of K2CO3 with mineral matter in the raw coal formed water-insoluble potassium compounds, such as potassium aluminosilicates, and reduced the catalytic activity, whereas no such negative reactions occurred for the HyperCoals. The steam gasification of the HyperCoals with K2CO3 was also determined to be favorable for the high-yield production of hydrogen. From these experimental results, the catalytic steam gasification of HyperCoal would potentially be a more efficient process for the production of hydrogen in the future.