Straws are agricultural residues that can be used to produce biomethane by anaerobic digestion. The methane yield of rice straw is lower than other straws. Steam explosion was investigated as a pretreatment to increase methane production. Pretreatment conditions with varying reaction times (12–30 min) and maximum temperatures (162–240 °C) were applied. The pretreated material was characterized for its composition and thermal and morphological properties. When the steam explosion was performed with a moderate severity parameter of S0 = 4.1 min, the methane yield was increased by 32% compared to untreated rice straw. This study shows that a harsher pretreatment at S0 > 4.3 min causes a drastic reduction of methane yield because inert condensation products are formed from hemicelluloses.