Within the global challenge of climate change and energy security, hydrogen is considered as a promising decarbonized energy vector to be used in electricity production and transportation. In this paper, the thermo-chemical production of hydrogen by natural gas reforming and by lignocellulosic biomass gasification are analyzed, compared and optimized by developing thermo-economic models. Combining flowsheeting with process integration techniques, thermo-economic analysis and life cycle assessment (LCA), a systematic comparison of different process options with regard to energy, economic and environmental considerations is made. The choice of the technologies is optimized together with the operating conditions using multi-objective optimization. In both natural gas and biomass based H2 pathways, a CO2 removal step is included during the H2 purification which allows for CO2 capture and further sequestration. The potential for greenhouse gas mitigation is assessed and compared with conventional plants without capture based on the CO2 avoidance cost and the overall CO2 equivalent emissions computed from the life cycle chain. The system’s performance is improved by introducing process integration valorizing the waste heat by the combined production of heat and power. The H2 application purpose and the corresponding required purity are key factors defining the process performance. The trade-offs between competing thermoenvironomic (i.e. energy, economic and environmental) objectives are finally assessed using a multi-objective optimization. For natural gas based H2 production overall energy efficiencies up to 80% and production cost of 22-110 USD/MWH2 are computed compared to around 60% efficiency and 75-263 USD/MWhH2 for biomass based processes having the advantage of using renewable resources. The CO2eq emissions are reduced by more than 6.4kgCO2eq/kgH2 for NG and 20kgCO2eq/kgH2 for BM processes compared to the cases without CO2 capture. The competitiveness on the energy market depends strongly on the resource price and on the imposed CO2 taxes. Our study shows that the thermo-chemical hydrogen production has to be analyzed as a polygeneration unit producing not only hydrogen but also captured CO2 and electricity.