Two approaches are presented to the modular construction of alkanethiolate self-assembled monolayers (SAMs) on gold surfaces selectively decorated with metalloporphyrins. In the first approach, a isonicotinate ligand is incorporated into the SAM via deposition from a two-component solution. In the second approach, a pyridine or imidazole ligand is attached to the SAM after self-assembly via carbodiimide-induced amide linkages to terminal carboxylates. Subsequent derivatization of monolayers formed in either of these ways with metalloporphyrins of the type Ru(POR)(CH3CN)(2), where POR = octaethylporphyrin or mesotetratoluylporphyrin, creates apically bound metalloporphyrins that exhibit sharp, stable cyclic voltammetric features in methylene chloride or water under ambient atmosphere. The presence of hexafluorophosphate in the supporting electrolyte is critical in evincing near-ideal electrochemistry. While the identity of the distal axial ligand under ambient atmosphere is unknown, this ligand can be readily and irreversibly exchanged with pyridine or other heterocyclic nitrogen donors. These approaches can be used to create previously unavailable asymmetrically substituted metalloporphyrins which can function as templates for additional modular modification of the monolayer/solution interface.