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Industrial expansion and increased water consumption have created water scarcity concerns. Meanwhile, conventional wastewater purification methods have failed to degrade recalcitrant pollutants efficiently. The present review paper discusses the recent advances and challenges in photocatalytic processes applied for industrial effluents treatment, with respect to phenolic compounds degradation. Key operational parameters including the catalyst loading, light intensity, initial pollutants concentration, pH, and type and concentrations of oxidants are evaluated and discussed. Compared to the other examined controlling parameters, pH has the highest effect on the photo-oxidation of contaminants by means of the photocatalyst ionization degree and surface charge. Furthermore, major phenolic compounds derived from industrial sources are comprehensively presented and the applicability of photocatalytic processes and the barriers in practical applications, including high energy demand, technical challenges, photocatalyst stability, and recyclability have been explored. The importance of energy consumption and operational costs for realistic large-scale processes are also discussed. Finally, research gaps in this area and the suggested direction for improving degradation efficiencies in industrial applications are presented. In the light of these premises, selective degradation processes in real water matrices such as untreated sewage are proposed.