A prescription verification system includes a database that contains a plurality of spectral signatures corresponding to identified pharmaceuticals. A multimodal multiplex sampling (MMS) spectrometer obtains a spectra of a pharmaceutical to be identified and verified. The pharmaceutical can be inside or out of a vial. The prescription verification system includes algorithms for matching spectra of pharmaceuticals to be verified obtaining using the MMS spectrometer to spectral signatures contained in the database corresponding to identified pharmaceuticals. The prescription verification system further includes algorithms for identifying such pharmaceuticals to be verified.