UV resonance Raman microspectroscopy was applied for a localization of the antiplasmodial naphthylisoquinoline alkaloid dioncophylline A in very low concentrations in different parts of the samples (e.g., in the roots) of the tropical liana Triphyophyllum peltatum. The application of resonance Raman microspectroscopy was characterized by a very high sensitivity and selectivity. It was possible to assign the resonance Raman spectra of dioncophylline A, dioncophylline C, and dioncopeltine A by means of a combination of NIR Raman spectroscopy and DFT calculations. The UV resonance Raman spectra of T. peltatum are very well resembled by the spectra of dioncophylline A, while they can be clearly distinguished from the spectra of dioncophylline C and dioncopeltine A. This distinction between the various naphthylisoquinolines was possible by the two modes at 1356 and 1613 cm-1. These two modes were assigned to C=C stretching and CH bending vibrations. The presented results of a highly sensitive and selective in situ localization of the active agent dioncophylline A in different parts of the plant material of T. peltatum are of high importance for the acquisition of new antimalarials and for plant science in general.