Sterically encumbering m-terphenyl isocyanides are a class of metal-binding group that foster low-coordinate metal-center environments in coordination chemistry by exerting considerable intermolecular steric pressures between neighboring ligands. In the context of metal surfaces, the encumbering steric properties of the m-terphenyl isocyanides are shown to weaken the interaction between the metal-binding group and a planar substrate, leading to a preference for molecular adsorption at sites with convex curvature, such as the step edges and herringbone elbow sites on Au(111). Here, we investigate the site-selective binding of individual m-terphenyl isocyanide ligands on a Au(111) surface through scanning tunneling microscopy (STM) and inelastic electron tunneling spectroscopy (IETS). The site-dependent steric pressure alters the vibrational fingerprint of the m-terphenyl isocyanides, which is characterized with single-molecule precision through joint experimental and theoretical approaches. This study for the first time provides molecular-level insights into the steric-pressure-enabled surface binding selectivity as well as its effect on the chemical properties of individual m-terphenyl isocyanide ligands, thereby highlighting the potential to control the physical and chemical properties of metal surfaces through tailored ligand design.