A molecular monocationic dyad comprising a borondipyrromethene (Bodipy) and an expanded planar acridinium cation was prepared. The dyad, when excited in solution by an ultrashort laser pulse, generates a charge‐shift state, where a positive charge is transferred to the Bodipy from the acridinium subunit. The process takes less than 1 ps in MeCN and around 8 ps in 1,2‐dichloroethane. The charge‐shift state collapses, in part, back to the ground state but it also leads to partial triplet formation; the discrimination between rates for the forward and reverse processes is circa 7.