Nanosized titanium dioxide (TiO2) nanoparticles were used for the photocatalytic reduction of hexavalent chromium in the presence of formic acid. The photoreduction of Cr(VI) in the absence of formic acid was quite slow. When formic acid was added in the chromium solution as the hole scavenger, a rapid photocatalytic reduction of Cr(VI) was observed, owing to the consumption of hole and the acceleration of the oxidation reaction. Furthermore, three commercial TiO2 nanoparticles (AEROXIDE® P25; Ishihara Sangyo ST-01; FUJIFILM Wako Pure Chemical Corp.) were evaluated for the photoactivity of reduction of Cr(VI).