The ability to study the interactions of hydrocarbons on carbon surfaces is an integral step toward gaining a molecular level understanding of the chemical reactions and physical properties occurring on them. Here, we apply vibrational sum frequency generation (SFG) to determine the tilt angle of toluene, a common organic solvent, on millimeter-thick highly oriented pyrolytic graphite (HOPG). The combination of a time-delay technique, which results in the successful suppression of the nonresonant SFG response, and a null angle method is shown to overcome the “strong optical absorber” problem posed by macroscopically thick carbon samples and yields a molecular tilt angle of toluene in the range of 37° to 42° from the surface normal. The implications of this approach for determining the orientation of organic species adsorbed on carbon interfaces, which are important for energy-relevant processes, are discussed.