The synthesis of new trans A(2)B(2)-substituted porphyrins bearing oxygenic substituent (methoxy, acetoxy, hydroxy) at the periphery of the ring are described. All of the synthesized products were characterized by (1)H-N.M.R., (13)C-N.M.R., and H.R.M.S. Electrochemical studies revealed two one-electron oxidations and two reductions. In addition, the X-ray structure of one methoxy-derivative was determined.