Mesostructured PbO/TiO materials were synthesized to perform electrocatalysis (as electrooxidation, EO) and photoelectrocatalysis for removing diclofenac (DCF), 15 ppm concentration in 0.1 M NaSO solutions, at different pH conditions (3.0, 6.0 and 9.0) by applying 30 mA cm. Titania nanotubes (TiONTs)-based materials were prepared to synthetize with a massive PbO deposit on this support to obtain TiONTs/PbO and a TiONTs:PbO material consisting in a dispersed PbO deposit on TiO-NTs that allowed the formation of a heterostructured surface of combined composition (TiO and PbO). Organics removal (DCF and byproducts) was monitored through UV-vis spectrophotometry and high-performance liquid chromatography (HPLC) during degradation tests. TiONTs/PbO electrode was tested in both processes, removing DCF at neutral and alkaline solution conditions in EO while an unimportant photoactivity was registered at this material. Conversely, TiONTs:PbO was used as electrocatalytic material in EO experiments, achieving more than 50% of DCF removal at pH 6.0 by applying 30 mA cm. Also, for first time, the synergic effect was investigated when it was exposed to UV irradiation in photoelectrocatalytic experiments, enhancing its efficacy (⁓more than 20%) to remove DCF from a solution with 15 ppm over performance removals achieved (56%) when EO was applied under similar conditions. Chemical Oxygen Demand (COD) analyses showed that significantly higher DCF degradation is reached under photoelectrocatalysis, since COD values decrease a 76% against a 42% decrease achieved with electrocatalysis. Scavenging experiments showed a significant participation on the pharmaceutical oxidation process through the generation of photoholes (h), hydroxyl radicals and sulfate-based oxidants.