Time-resolved absorption spectroscopy was used to study the femtosecond and picosecond time scale electron injection from the excited singlet and triplet states of Ru(dcbpY)(2)(NCS)(2) (RuN3) into titanium dioxide (TiO2) nanocrystalline particle film in acetonitrile. The fastest resolved time constant of similar to30 fs was shown to reflect a sum of two parallel ultrafast processes, nonergodic electron transfer (ET) from the initially excited singlet state of RuN3 to the conduction band of TiO2 and intersystem crossing (ISC). The branching ratio of 1.5 between the two competing processes gives rate constants of 1/50 fs(-1) for ET and 1/75 fs(-1) for ISC. Following the ultrafast processes, a minor part of the electron injection (40%) occurs from the thermalized triplet state of RuN3 on the picosecond time scale. The kinetics of this slower phase of electron injection is nonexponential and can be fitted with time constants ranging from similar to1 to similar to60 ps.