The current study deals with Cr(VI) removal using a polymer-nano metal oxide based composite film under fluorescent light condition. This was prepared by the layer-by-layer coating of chitosan/polyethylene glycol (PEG) blend, polystyrene sulphate (PSS) and nanotitania/nanoalumina mixture respectively on the glass slide. The Taguchi’s orthogonal array (L 25 ) design was employed for determining the optimal process factors (pH: 6, reaction time: 10min and initial Cr(VI) concentration: 20mgL −1 ) and the film preparation factors (dosage of PEG: 0.5 v/v%, dosage of PSS: 0.25 v/v%, dosage of nanotitania–nanoalumina mixture: 95:5mgL −1 ). The maximum removal capacity observed at the optimal conditions was 278.9±4.3mgg −1 . The SEM–EDX, XPS, FTIR–ATR spectra confirmed the photocatalytic reduction of Cr(VI) and binding of Cr(III) species on the PSS layer. A 97% regeneration of the film and a cumulative removal capacity of 2467.6mgg −1 were observed after nine cycles of reuse. This removal capacity for chromium is about twenty fold higher than that reported by any single nanoparticle so far.