Billions of litres of wastewater are produced daily from domestic and industrial areas, and whilst wastewater is often perceived as a problem, it has the potential to be viewed as a rich source for resources and energy. Wastewater contains between four and five times more energy than is required to treat it, and is a potential source of bio-hydrogen—a clean energy vector, a feedstock chemical and a fuel, widely recognised to have a role in the decarbonisation of the future energy system. This paper investigates sustainable, low-energy intensive routes for hydrogen production from wastewater, critically analysing five technologies, namely photo-fermentation, dark fermentation, photocatalysis, microbial photo electrochemical processes and microbial electrolysis cells (MECs). The paper compares key parameters influencing H₂ production yield, such as pH, temperature and reactor design, summarises the state of the art in each area, and highlights the scale-up technical challenges. In addition to H₂ production, these processes can be used for partial wastewater remediation, providing at least 45% reduction in chemical oxygen demand (COD), and are suitable for integration into existing wastewater treatment plants. Key advancements in lab-based research are included, highlighting the potential for each technology to contribute to the development of clean energy. Whilst there have been efforts to scale dark fermentation, electro and photo chemical technologies are still at the early stages of development (Technology Readiness Levels below 4); therefore, pilot plants and demonstrators sited at wastewater treatment facilities are needed to assess commercial viability. As such, a multidisciplinary approach is needed to overcome the current barriers to implementation, integrating expertise in engineering, chemistry and microbiology with the commercial experience of both water and energy sectors. The review concludes by highlighting MECs as a promising technology, due to excellent system modularity, good hydrogen yield (3.6–7.9 L/L/d from synthetic wastewater) and the potential to remove up to 80% COD from influent streams.