Ultrafast nuclear driven charge transfer prior to dissociation is an important process in modular systems as was demonstrated experimentally in the bifunctional molecule 2-phenylethyl-N,N-dimethylamine (PENNA) in work by Lehr et al. (J. Phys. Chem. A 2005, 109, 8074). The ultrafast dynamics of PENNA photo excited to the three lowest electronic states of the cation (D-0, D-1, and D-2) was studied using quantum chemistry and surface hoping. We show that a conical intersection, localized in the Franck-Condon region, between the D-0 and the D-1 states, leads to an ultrafast charge transfer, computed here to be on a time scale of 65 fs, between the phenyl and the amine charged subunits. On the D-0 ground state, the dissociation proceeds on the 60 ps time scale through a 19 kcal/mol late barrier. The computed kinetic energy release is in good agreement with a new experimental measurement of PENNA ionization by an 800 nm 30 fs intense laser pulse.