Reduced graphene oxide (rGO)–zinc oxide (ZnO) composites were synthesized by a two-step hydrolysis–calcination method, using GO and Zn(Ac)2 as precursors. The structure and morphology of the as-prepared samples were characterized by thermogravimetric analysis, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and field emission scanning electron microscopy. It was shown that the well-dispersed ZnO nanoparticles (NPs) were deposited on rGO homogeneously. So far as ZnO NPs with different diameters were synthesized in the varied samples, the ZnO NPs with an average diameter of around 10 nm which were obtained at the heating temperature of 300 °C for 4 h exhibited higher photocatalytic activity than the others. A relatively low amount of rGO–ZnO composites (5 mg) demonstrated enhanced photocatalytic activity to decompose methyl orange (MO, 40 mg L−1) and methylene blue (MB, 10 mg L−1) under low-power ultraviolet light. Furthermore, rGO–ZnO composites exhibited high sensitivity, and a response can be achieved at 50.09 to 1000 ppm acetone. In addition, the ultraviolet light-induced photocatalytic mechanism as well as gas sensing mechanism was also discussed. Both rGO and crystallinity played important roles in improving photocatalytic activity and gas sensing properties.