The inhomogeneous interfacial electron transfer (IET) dynamics of 9-phenyl-2,3,7-trihydroxy-6-fluorone (PF)-sensitized TiO(2) nanoparticles (NPs) has been probed by a single-molecule photon-stamping technique as well as ensemble-averaged femtosecond transient absorption spectroscopy. The forward electron transfer (FET) time shows a broad distribution at the single-molecule level, indicating the inhomogeneous interactions and ET reactivity of the PF/TiO(2) NP system. The broad distribution of the FET time is measured to be 0.4 +/- 0.1 ps in the transient absorption and picoseconds to nanoseconds in the photon-stamping measurements. The charge recombination time, having a broad distribution at the single-molecule level, clearly shows a biexponential dynamic behavior in the transient absorption: a fast component of 3.0 +/- 0.1 ps and a slow component of 11.5 +/- 0.5 ns. We suggest that both strong and weak interactions between PF and TiO(2) coexist, and we have proposed two mechanisms to interpret the observed IET dynamics. A single-molecule photon-stamping technique and ensemble-averaged transient absorption spectroscopy provide efficient "zoom-in" and "zoom-out" approaches for probing the IET dynamics. The physical nature of the observed multiexponential or stretched-exponential ET dynamics in the ensemble-averaged experiments, often associated with dynamic and static inhomogeneous ET dynamics, can be identified and analyzed by single-molecule spectroscopy measurements.