We report the use of electrical measurements to identify simultaneously the number and type of organic molecules within metal-molecule-metal junctions. Our strategy combines analyses of single-molecule conductance and inelastic electron tunneling spectra, exploiting a nanofabricated mechanically controllable break junction. We found that the peak linewidth of the inelastic electron tunneling spectrum decreased as the modulation voltage and temperature decreased, and that the selection rule for inelastic electron tunneling spectroscopy agrees with that for Raman spectroscopy. Furthermore, the differential conductance curve of the single-molecule junction suggests that it has asymmetrical electrode-molecule coupling.