Understanding the charge transport properties in general of different molecular components in a self-assembled monolayer (SAM) is of importance for the rational design of SAM molecular structures for molecular electronics. In this study, we study an important aspect of the charge transport properties, i.e. the charge transfer (CT) dynamics between the active molecular component (in this case, the ferrocenyl moieties of a ferrocenyl-n-alkanethiol SAM) and the electrode using synchrotron-based core-hole clock (CHC) spectroscopy. The characteristic CT times are found to depend strongly on the character of the ferrocenyl-derived molecular orbitals (MOs) which mediate the CT process. Furthermore, by systemically shifting the position of the ferrocenyl moiety in the SAM, it is found that the CT characteristics of the ferrocenyl MOs display distinct dependence on its distance to the electrode. These results demonstrate experimentally that the efficiency and rate of charge transport through the molecular backbone can be modulated by resonant injection of charge carriers into specific MOs.