The effect of devolatilization conditions (pressure and temperature) on the steam gasification kinetics and reactivity of coal chars was investigated. For this purpose, five different rank coals were selected: a lignite (LT), two high-volatile bituminous coals (DT and SA), a low-volatile bituminous coal (DI), and a semianthracite (HV). The coal chars were obtained by devolatilization in a novel pressurized fixed-bed reactor at temperatures of 800, 900, and 1000 degrees C and pressures of 1, 5, 10, and 20 atm. The reactivity of the chars was studied by isothermal thermogravimetric analysis in a kinetically controlled regime at different temperatures under a steam atmosphere. The reactive behavior of the chars was evaluated by means of the random pore model (RPM), which satisfactorily described the steam gasification of the coal chars. The gasification apparent reaction rate increased as the devolatilization pressure increased, whereas this parameter decreased as the devolatilization temperature increased.