Graphene oxide (GO) nanosheets and polyoxometalate clusters, H ₃PW₁₂O₄₀ (PW), were co-assembled into multilayer films via electrostatic layer-by-layer assembly. Under UV irradiation, a photoreduction reaction took place in the films which converted GO to reduced GO (rGO) due to the photocatalytic activity of PW clusters. By this means, uniform and large-area composite films based on rGO were fabricated with precisely controlled thickness on various substrates such as quartz, silicon, and plastic supports. We further fabricated field effect transistors based on the composite films, which exhibited typical ambipolar features and good transport properties for both holes and electrons. The on/off ratios and the charge carrier mobilities of the transistors depend on the number of deposited layers and can be controlled easily. Furthermore, we used photomasks to produce conductive patterns of rGO domains on the films, which served as efficient microelectrodes for photodetector devices.