Intramolecular charge separation in the donor- bridge- acceptor molecule 4-(9-Anthrylmethyl)-N-methyl-pyridinium-tetrafluoroborate has been verified evolving in consecutive steps of excited states on sub-picosecond time scale. In the first step an excited anthracene intermediate and in the second an ionic anthracene state is formed, identified by its transient absorption. Instead, in systems with polyene as a bridge the formation of the anthracene radical state is modified by increased coupling strength of the molecular subunits.