The gasification of biomass in supercritical water is a promising technology for hydrogen production and the paper reports a thermodynamic analysis, based on minimization of Gibbs free energy, of the gasification with supercritical water of different biomass and agro-food residues: almond shells, digestate from wastewater treatment, algae and manure sludge. Numerical simulations were performed in order to assess the effect of temperature, pressure and biomass-to-water ratio on gas-phase yield and composition.A partial energy integration was also discussed, by considering the energy recovery from a turbine expansion of the gas-phase stream leaving the gasifier. The proposed thermodynamic approach allows predicting not only gasification efficiency of gasifier but also energy balance on the entire gasification process. Results showed that the dry substrates (almond shells and algae more than digestate and sludge) tend to form more carbon monoxide. Besides, data comparison revealed that the produced hydrogen comes from biomass and water for high process temperature, while when temperature decreases, the thermodynamic path tends to promote water formation from the hydrogen of the dry biomass.