An ionic liquid, namely imidazolium sulfonic acid chloride (ISAC) has been electrostatically grafted over cerium oxide nanoparticles to produce a nanocomposite, nano‐CeO2‐IL. The as‐prepared composite was characterized by various analytical techniques such as XRD, FT‐IR, SEM, TEM, XPS, BET, UV‐DRS, PL, and TGA to confirm the grafting of ISAC over CeO2 NPs. The photocatalytic process is regarded as the method of choice for the elimination of air pollutants because of its great efficiency and relatively benign working conditions. According to UV‐DRS spectra, its optical gap is 2.07 eV, which is appropriate for the visible light spectrum. The composite was investigated as a visible‐light‐driven photocatalyst for hydroxylation of benzene to phenol and heavy metal Cr (VI) reduction. Moreover, the scavenger experiments confirmed the detection of ⋅OH radicals which played a crucial role in the photocatalytic experiments. Within 60 minutes, 98.5 % of benzene was converted to phenol with 82.7 % selectivity in addition to 93.63 % Cr (VI) reduction within 30 mins. The photocatalytic reduction of Cr(VI) to Cr(III) follows a first‐order model with a rate constant of 0.027 min−1. The remarkably high photocatalytic performance of the catalyst may be ascribed to the synergistic interaction between the nano‐CeO2 catalyst and ionic liquid.