A comparative life cycle assessment (LCA) of two solar-driven advanced oxidation processes, namely heterogeneous semiconductor photocatalysis and homogeneous photo-Fenton, both coupled to biological treatment, is carried out in order to identify the environmentally preferable alternative to treat industrial wastewaters containing non-biodegradable priority hazardous substances. The study is based on solar pilot plant tests using alpha-methyl-phenylglycine as a target substance. The LCA study is based on the experimental results obtained, along with data from an industrial-scale plant. The system under study includes production of the plant infrastructure, chemicals, electricity, transport of all these materials to the plant site, management of the spent catalyst by transport and landfilling, as well as treatment of the biodegradable effluent obtained in a conventional municipal wastewater treatment plant, and excess sludge treatment by incineration. Nine environmental impact categories are included in the LCA: global warming, ozone depletion, human toxicity, freshwater aquatic toxicity, photochemical ozone formation, acidification, eutrophication, energy consumption, and land use. The experimental results obtained in the pilot plant show that solar photo-Fenton is able to obtain a biodegradable effluent much faster than solar heterogeneous photocatalysis, implying that the latter would require a much larger solar collector area in an industrial application. The results of the LCA show that, an industrial wastewater treatment plant based on heterogeneous photocatalysis involves a higher environmental impact than the photo-Fenton alternative, which displays impact scores 80-90% lower in most impact categories assessed. These results are mainly due to the larger size of the solar collector field needed by the plant.