Two electrolysis technologies fed with renewable energy sources are promising for the production of CO₂-free hydrogen and enabling the transition to a hydrogen society: Alkaline Electrolyte (AE) and Polymer Electrolyte Membrane (PEM). However, limited information exists on the potential environmental impacts of these promising sustainable innovations when operating on a large-scale. To fill this gap, the performance of AE and PEM systems is compared, using ex-ante Life Cycle Assessment (LCA), technology analysis and exploratory scenarios for which a refined methodology has been developed to study the effects of implementing large-scale sustainable hydrogen production systems. Ex-ante LCA allows modelling the environmental impacts of hydrogen production, exploratory scenario analysis allows modelling possible upscaling effects at potential future states of hydrogen production and use in vehicles in the Netherlands in 2050. A bridging tool for mapping the technological field has been created enabling the combination of quantitative LCAs with qualitative scenarios. This tool also enables diversity for exploring multiple sets of visions. The main results from the paper show, with an exception for the “ozone depletion” impact category, (1) that large-scale AE and PEM systems have similar environmental impacts with variations lower than 7% in all impact categories, (2) that the contribution of the electrolyser is limited to 10% of all impact categories results, and (3) that the origin of the electricity is the largest contributor to the environmental impact contributing to more than 90% in all impact categories, even when renewable energy sources are used. It is concluded that the methodology was applied successfully and provides a solid basis for an ex-ante assessment framework that can be applied to emerging technological systems.