The preparation of immobilized graphene–based photocatalyst layers is highly desired for environmental applications. In this study, the preparation of an immobilized reduced graphene oxide (rGO)/TiO₂ composite by electrophoretic deposition (EPD) was optimized. It enabled quantitative deposition without sintering and without the use of any dispersive additive. The presence of rGO had beneficial effects on the photocatalytic degradation of 4-chlorophenol in an aqueous solution. A marked increase in the photocatalytic degradation rate was observed, even at very low concentrations of rGO. Compared with the TiO₂ and GO/TiO₂ reference layers, use of the rGO/TiO₂ composite (0.5 wt% of rGO) increased the first-order reaction rate constant by about 70%. This enhanced performance was due to the increased formation of hydroxyl radicals that attacked the 4-chlorophenol molecules. The direct charge transfer mechanism had only limited effect on the degradation. Thus, EPD-prepared rGO/TiO₂ layers appear to be suitable for environmental application.