Abstract The chemical immobilization of a dibenzoic acid oligo (phenylene vinylene) (OPV) derivative for TiO 2 sensitization was evaluated as a strategy to enhance both the stability and photocatalytic performance of this π‐conjugated moiety when applied to the photodegradation of indigo carmine dye (IC) as model pollutant. The results show that the electron injection from the photoexcited OPV to the TiO 2 conduction band remarkably boosts the IC degradation ability under visible light illumination. The use of SiO 2 as non‐photoactive support was also investigated to simultaneously determine the role of the inorganic support in the photocatalytic process. The spectroscopic, thermal, and surface characterization validated the successful grafting of the OPV to the inorganic supports. Moreover, superoxide radical and singlet oxygen were established as the active species involved in the dye degradation identifying an additional direct reducing pathway. Interestingly, the use of electron donors proved to be an ineffective approach to increase the system performance, entailing that the OPV regeneration proceeds chiefly via back electron transfer processes. Finally, the reusability tests confirmed that TiO 2 /OPV material retains up to 86 % of their photocatalytic activity during the first five cycles, demonstrating a critical enhancement in the organic conjugated framework stability.