A highly sensitive and selective sunlight-driven photoelectrochemical sensor for the direct detection and reduction of chromium(VI) was developed based on single crystal rutile titanium dioxide nanorods decorated with gold nanoparticles. Under sun simulator illumination via the amperometric technique, these Au decorated TiO2 photoelectrodes exhibited the highest sensitivity (13.94 μA μM−1) ever reported among Au-based electrodes for Cr(VI) detection, with a very low detection limit (S/N = 3) of 0.006 μM and wide linear concentration range from 0.01 μM to 50 μM. Measurements in real water samples such as laboratory and river water also showed excellent anti-interference and recovery capabilities.