Heterostructures based on Fe2O3/CeO2 were synthesized by coprecipitating iron and cerium salts, with 70% and 50% atomic percentage of iron, and heat treatment at 600 and 800 °C (Fe70Ce600, Fe50Ce600, Fe70Ce800, Fe50Ce800). The catalytic activity in the Fenton and photo-Fenton process was evaluated in the degradation of venlafaxine (VEN) using UV/Vis LEDs. Treatment at 800 °C promoted greater crystallinity, increased crystallite size, decreased specific area, high absorption between 200 - 600nm, and bandgap energy (Eg) between 1.6 and 3.0eV. The heat treatment promoted different mechanisms in heterostructure materials with type I (straddling) schemes for Fe70Ce600 and Fe50Ce600, type II for Fe50Ce800, and direct Z for Fe70Ce800 responsible for generating a higher concentration of HO• radicals, high oxidation-reduction power (Fe2+/Fe3+) and (Ce4+/Ce3+), greater effective separation of charge carriers, providing improved catalytic activity due to the synergy between heterogeneous photocatalysis and photo-Fenton processes. LC-MS/MS analysis identified 12 transformation products (TPs), involving hydroxylation reactions, demethylation, and loss of cyclohexanol. The transformation products TP2 and TP9 were exclusive to Fe70Ce800, confirming different mechanisms among the heterostructures.