The four porphodimethene isomers, 5,10- and 5,15-disubstituted, have been synthesized in a one-pot reaction by the Lindsey protocol. Three of them have been characterized by X-ray crystallography. Structures show that two of them are 5,15-porphodimethenes: one is syn-equatorial, another is anti-configuration; the third one is 5,10-porphodimethene. In the 5,10-porphodimethene, the tripyrrane subunit remains planar conformation. 1H NMR and UV-vis spectra have also been characterized. Both spectra reveal remarkable difference between 5,10- and 5,15-disubstituted isomers.