Wide bandgap semiconductors-based photocatalysts are usually limited by their low solar energy conversion efficiency due to their limited absorption solar wavelength, surface’s fast recombination of photoelectron–hole pairs and low charge-carrier mobility. Here we report a new stepwise solution synthesis for making a new photocatalytic core/shell of titanate nanowire/reduced graphene oxide shell (or titanate/rGO) 1D-nanocomposite. The new core/shell nanocomposite maximized the specific surface area, largely reduced the charge transfer resistance and reaction energy barrier, and significantly improved the absorption of the visible light. The core/shell nanocomposites’ large on/off current ratio and rapid photo-responses boosted the photocurrent by 30.0%, the photocatalysis rate by 50.0%, and the specific surface area by 16.4%, when comparing with the pure titanate nanowire core. Our numerical simulations support the effective charge separation on the new core-shell nanostructure, which can help further advance the new photocatalysis.