Graphene-CdS (GR-CdS) nanocomposites were prepared in a one-step synthesis in aqueous solution. The synthetic approach was simple and fast, and it may be extended for the synthesis of other GR-metal-sulfide nanocomposites. The as-prepared GR-CdS nanocomposite films inherited the excellent electron-transport properties of GR. In addition, the heteronanostructure of the GR-CdS nanocomposites facilitated the spatial separation of the charge carriers, thus resulting in enhanced photocurrent intensity, which makes it a promising candidate for photoelectrochemical applications. This strategy was used for the fabrication of an advanced photoelectrochemical cytosensor, based on these GR-CdS nanocomposites, by using a layer-by-layer assembly process. This photoelectrochemical cytosensor showed a good photoelectronic effect and cell-capture ability, and had a wide linear range and low detection limit for Hela cells. The as-synthesized GR-CdS nanocomposites exhibited obviously enhanced photovoltaic properties, which could be an efficient platform for many other high-performance photovoltaic devices.