Simultaneous application of solar photo-Fenton and ozonation (SPFO) for the efficient treatment of real wastewaters was studied. Four different industrial effluents were selected for the study: landfill leachate, pharmaceutical effluent and two textile wastewaters, in order to demonstrate the effectiveness and versatility of the proposed technology. SPFO performance was compared with individual processes (either solar photo-Fenton or ozonation), as well as the hybrid Fenton and ozonation treatment. In highly polluted wastewaters, combined strategies led to higher organic matter removal than O3 and photo-Fenton processes applied individually. Solar light favoured catalyst regeneration, allowing removal efficiencies up to 67% of chemical oxygen demand (COD) and 62% of total organic carbon (TOC) (in the case of textile wastewaters) using an initial concentration of only 10 mg Fe2+ L−1. The reduction of catalyst consumption, along with the absence of sludge production (since Fe2+ removal from the effluent is not required), led to a significant decrease in operational costs (up to 1.22 € kg−1 COD removed) when combined Fenton and ozonation was applied under solar light. SPFO results in a versatile, effective and economically efficient technology, thus postulating as a promising alternative for reducing the organic load of highly polluted industrial effluents prior to biological treatment.