Synthesis of Rhenium(I) bridged three cyclic dyads containing two 21-thiaporphyrins or two 21-oxaporphyrins or one 21-thia and one 21-oxaporphyrin using cis-pyridyl 21-thia and 21-oxaporphyrin building blocks is reported. The fluorescence properties studied by both steady state and time-resolved fluorescence techniques on dyad containing one 21-thia and one 21-oxaporphyrin unit indicated a possibility of energy transfer from 21-oxaporphyrin unit to 21-thiaporphyrin unit. © 2005 Elsevier B.V. All rights reserved.