Electric field-assisted charge carrier photogeneration in a ladder-type methyl-substituted poly(paraphenylene) was investigated by ultrafast absorption spectroscopy at low excitation intensity. The dissociation of excitons into electron-hole pairs occurs from the vibrationally relaxed excited state throughout its lifetime and is caused by the applied electric field, rather than by existence of special "dissociation sites." These findings are of importance for material choice in device applications.