An indirect photoelectrochemical sensing platform for toxic hexavalent chromium was for the first time constructed based on its redox reaction with quercetin as both the electron donor and photosensitizer on a TiO(2) photoanode, and thus inhibiting the photocurrent quantitatively and selectively. The presence of even 500-fold coexisting Cr(III) does not interfere in the detection of Cr(VI). Under the optimum conditions, the electrode displayed a linear decrease response as the Cr(VI) concentration increased from 1 to 10 nmol L(-1) and from 20 to 140 nmol L(-1) with a detection limit of 0.24 nmol L(-1). Many possible ions in drinking water did not interfere with the detection, and the real sample detection results agreed well with those obtained by GFAAS. This work provide a novel methodology for the simple, low-cost photoelectrochemical detection of Cr(VI) in drinking water.