Metal-organic coordination structures at interfaces play an essential role in many biological and chemical systems. Understanding the molecular specificity, orientation, and spatial distribution of the coordination complexes at the nanometer scale is of great importance for effective molecular engineering of nanostructures and fabrication of functional devices with controllable properties. However, fundamental properties of such coordination systems are still rarely studied directly. In this work, we present a spectroscopic approach on the basis of tip-enhanced Raman spectroscopy (TERS) to investigate cobalt(II) tetraphenyl-porphyrine coordination species on the scale of a single molecule under ambient conditions. Coordination species anchored on gold surfaces modified with pyridine thiol self-assembled monolayers can be spectroscopically distinguished and mapped with ca. 2 nm resolution. In addition, in combination with density functional theory simulations, the adsorption configuration and molecular orientation of the coordination complexes are also revealed using TERS imaging.