Supercritical water gasification (SCWG) technology is highly promising for its ability to cleanly and efficiently convert biomass to hydrogen. This paper developed a model for the gasification of rice straw in supercritical water (SCW) to predict the direction and limit of the reaction based on the Gibbs free energy minimization principle. The equilibrium distribution of rice straw gasification products was analyzed under a wide range of parameters including temperatures of 400–1200 °C, pressures of 20–50 MPa, and rice straw concentrations of 5–40 wt%. Coke may not be produced due to the excellent properties of supercritical water under thermodynamic constraints. Higher temperatures, lower pressures, and biomass concentrations facilitated the movement of the chemical equilibrium towards hydrogen production. The hydrogen yield was 47.17 mol/kg at a temperature of 650 °C, a pressure of 25 MPa, and a rice straw concentration of 5 wt%. Meanwhile, there is an absorptive process in the rice straw SCWG process for high-calorific value hydrogen production. Energy self-sufficiency of the SCWG process can be maintained by adding small amounts of oxygen (ER < 0.2). This work would be of great value in guiding rice straw SCWG experiments.