The dynamics of the transfer of electrons stored in TiO2 nanoparticles to Cr(VI) in aqueous solution have been investigated using the stopped flow technique. TiO2 nanoparticles were previously irradiated under UV light in the presence of formic acid, and trapped electrons (e(trap)(-)) were made to react with Cr(VI) as acceptor species; other common acceptor species such as O2 and H2O2 were also tested. The temporal evolution of the number of trapped electrons was followed by the decrease in the absorbance at 600 nm, and the kinetics of the electron-transfer reaction was modeled. Additionally, the rate of formation of the surface complex between Cr(VI) and TiO2 was determined with the stopped flow technique by following the evolution of the absorbance at 400 nm of suspensions of nonirradiated TiO2 nanoparticles and Cr(VI) at different concentrations. An approximately quadratic relationship was observed between the maximum absorbance of the surface complex and the concentration of Cr(VI), suggesting that Cr(VI) adsorbs onto the TiO2 surface as dichromate. The kinetic analyses indicate that the electron transfer from TiO2 to Cr(VI) does not require the previous formation of the Cr(VI)-TiO2 surface complex, at least the complex detected here through the stopped flow experiments. When previously irradiated TiO2 was used to follow the evolution of the Cr(VI)-TiO2 complex, an inhibition of the formation of the complex was observed, which can be related to the TiO2 deactivation caused by Cr(III) deposition.