A polymeric composite consisting of Fe-N-codoped TiO2 (Fe-N-TiO2) dispersed into a monolithic syndiotactic polystyrene (sPS) aerogel (Fe-N-TiO2/sPS, 10/90 w/w) was used for the photocatalytic hydroxylation of benzene to phenol in presence of H2O2 to enhance the phenol selectivity and yield compared to Fe-N-TiO2 in powder form. Under UV light, Fe-N-TiO2/sPS composite aerogel showed selectivity to phenol of 43%, one order of magnitude more than the selectivity showed by Fe-N-TiO2 in powder form (4%). Under visible light irradiation Fe-N-TiO2 in powder form did not produce phenol, whereas selectivity to phenol of Fe-N-TiO2/sPS was 16%. The polymeric composite was recycled and reused up to five times without a significant decrease in photocatalytic oxidation activity in terms of benzene conversion and phenol yield, indicating the stability of the catalytic composite. Therefore, it was proved that the obtained photoreactive polymer composite could allow the development of innovative sustainable processes able to realize the selective oxidation reactions of aromatic hydrocarbons under mild conditions.