The dynamics of heterogeneous electron transfer ( ET) from the polycyclic aromatic chromophore perylene to nanostructured TiO2 anatase was investigated for two different anchor groups with transient absorption spectroscopy in an ultrahigh vacuum. Data from ultraviolet photoelectron spectroscopy and from linear absorption spectroscopy showed that the donor state of the chromophore was located around 900 meV above the lower edge of the conduction band. With the wide band limit fulfilled the rate of the heterogeneous ET reaction was only controlled by the strength of the electronic coupling and not reduced by Franck-Condon factors. Two different time constants for the electron transfer, i.e., 13 and 28 fs, were measured with carboxylic acid and phosphonic acid as the respective anchor groups. The difference in the ET time constants was explained with the different extension of the donor orbital onto the respective anchor group to reach the empty electronic states of the semiconductor. The time constants were extracted by means of a simple rate equation model. The validity of applying this model on this ultrafast time scale was verified by comparing the rate equation model with an optical Bloch equation model.