Mass analyzed threshold ionization (MATI) spectroscopy in connection with the two-color resonant two-photon excitation scheme was used to record the vibrationally resolved cation spectra of a variety of aromatic molecules. These spectra can be used as the fingerprints for identifying each cation species. Since the nature and the relative location of the substituent on the ring can influence the ionization threshold and the vibrational frequency, the obtained precise data lead us to have better insights into the vicinal substitution, isotope, heavy atom, conformational, long alky chain, and cyclization effects. These experimental findings are well supported by the ab initio and density functional theory calculations.