Bicyclo[2.2.2]octadiene-connected pyrrolo-porphyrins have been prepared by an inverse-type [3+1] porphyrin synthesis of a bicyclo[2.2.2]octadiene-fused dipyrrole with a tripyrrane dicarbaldehyde. Another [3+1] porphyrin synthesis of pyrrole-connected porphyrins with the same or other tripyrrane dicarbalde- hydes gave bicyclo[2.2.2]octadiene-bridged diporphyrins, the central metals and/or peripheral substituents of which were different. Thermal decomposition of the, bicyclo[2.2.2]octadiene skeleton to a benzene moiety gave pi-system-fused porphyrin dimers in a highly pure form.