The formation of porphyrin- and sapphyrin-containing self-assembled monolayers (SAMs) on electrochemically prepared gold surfaces by a multistep approach is described. After electrochemical preparation, the gold substrate was characterized by surface-enhanced Raman scattering (SERS) spectroscopy and cyclic voltammetry. SERS characterization was also used to study the basic architecture and properties of the porphyrin- and sapphyrin-modified SAMs and their interactions with model compounds, that is, fluoranthene, 1,10-phenanthroline, and adenine. The results obtained lead to the conclusion that in a general sense, macrocyclic oligopyrrole functionalized SAMs could prove useful in the analysis and detection of polyaromatic and heterocyclic compounds.