Interfacial electron transfer (IET) between a chromophore and a semiconductor nanoparticle is one of the key processes in a dye-sensitized solar cell. Theoretical simulations of the electron transfer in polyoxotitanate nanoclusters Ti17O24(OPri)(20) (Ti-17) functionalized with four p-nitrophenyl acetylacetone (NPA-H) adsorbates, of which the atomic structure has been fully established by X-ray diffraction measurements, are presented. Complementary experimental information showing IET has been obtained by EPR spectroscopy. Evolution of the time-dependent photoexcited electron during the initial 5 fs after instantaneous excitation to the NPA LUMO + 1 has been evaluated. Evidence for delocalization of the excitation over multiple chromophores after excitation to the NPA LUMO + 2 state on a 15 fs time scale is also obtained. While chromophores are generally considered electronically isolated with respect to neighboring sensitizers, our calculations show that this is not necessarily the case. The present work is the most comprehensive study to date of a sensitized semiconductor nanoparticle in which the structure of the surface and the mode of molecular adsorption are precisely defined.