As one of the main industrial segments of the current geoeconomics scenario, agro-industrial activities generate excessive amounts of waste. The gasification of such waste using supercritical water (SCWG) has the potential to convert the waste and generate products with high added value, hydrogen being the product of greatest interest. Within this context, this article presents studies on the SCWG processes of lignocellulosic residues from cotton, rice, and mustard husks. The Gibbs energy minimization (minG) and entropy maximization (maxS) approaches were applied to evaluate the processes conditioned in isothermal and adiabatic reactors, respectively. The thermodynamic and phase equilibria were written as a nonlinear programming problem using the Peng–Robinson state solution for the prediction of fugacity coefficients. As an optimization tool, TeS (Thermodynamic Equilibrium Simulation) software v.10 was used with the help of the trust-constr algorithm to search for the optimal point. The simulated results were validated with experimental data presenting surface coefficients greater than 0.99, validating the use of the proposed modeling to evaluate reaction systems of interest. It was found that increases in temperature and amounts of biomass in the process feed tend to maximize hydrogen formation. In addition to these variables, the H2/CO ratio is of interest considering that these processes can be directed toward the production of synthesis gas (syngas). The results indicated that the selected processes can be directed to the production of synthesis gas, including the production of chemicals such as methanol, dimethyl ether, and ammonia. Using an entropy maximization approach, it was possible to verify the thermal behavior of reaction systems. The maxS results indicated that the selected processes have a predominantly exothermic character. The initial temperature and biomass composition had predominant effects on the equilibrium temperature of the system. In summary, this work applied advanced optimization and modeling methodologies to validate the feasibility of SCWG processes in producing hydrogen and other valuable chemicals from agro-industrial waste.