The removal of dissolved organic carbon (DOC) and total polyphenols (TPh) from agro-industrial wastewater was evaluated via the application of coagulation–flocculation–decantation (CFD) and Fenton-based processes. For the CFD process, an organic coagulant based on Acacia dealbata Link. leaf powder (LP) was applied. The results showed that the application of the LP at pH 3.0, with an LP:DOC ratio of 0.5:1 (w/w), achieved a high removal of turbidity, total suspended solids (TSS), and volatile suspended solids (VSS) of 84.7, 79.1, and 76.6%, respectively. The CFD sludge was recycled as fertilizer in plant culture (germination index ≥ 80%). Afterwards, the direct application of Fenton-based processes to raw WW was assessed. The Fenton-based processes (UV/Fenton, UV/Fenton-like, and heterogeneous UV/Fenton) showed high energy efficiency and a cost of 1.29, 1.31 and 1.82 €/g/L DOC removal, respectively. The combination of both processes showed the near complete removal of TPh and DOC after 240 min of reaction time, with high energy efficiency. In accordance with the results obtained, the combination of CFD with Fenton-based processes achieves the legal limits for the disposal of water into the environment, thus allowing the water to be recycled for irrigation.