Gold-supported hybrid bilayers comprising phospholipids and alkanethiols have been found to be highly useful in biomembrane mimicking as well as biosensing ever since their introduction by Plant in 1993 (Plant, A. L. Langmuir 1993, 9, 2764-2767). Generalizing the mechanism (i.e., hydrophobic/hydrophobic interaction) that primarily drives bilayer formation, we report here that such a bilayer structure can also be successfully obtained when aromatic thiols are employed in place of alkanethiols. Four aromatic thiols were studied here (thiophenol, 2-naphthalene thiol, biphenyl-4-thiol, and diphenylenevinylene methanethiol), all affording reliable bilayer formation when 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine liposomes were incubated with self-assembled monolayers of these thiols. Characterization of the resultant structures, using cyclic voltammetry, impedance analysis, and atomic force microscopy, confirms the bilayer formation. Significant differences in electrochemical blocking and mechanical characteristics of these new bilayers were identified in comparison to their alkanethiol counterparts. Taking advantage of these new features, we present a new scheme for the straightforward biorecognition of a lipolytic enzyme (phospholipase A2) using these phospholipid/aromatic thiol bilayers.