Plant metabolites exhibit a variety of different chemical properties, physiological activities, and biological functions. However, untargeted imaging of highly diverse metabolic profiles is still a great challenge. Here, metabolites in plant leaves were imaged via imprint, followed by desorption electrospray ionization/post-photoionization (imprint DESI/PI) mass spectrometry imaging. In contrast to the traditional imprint DESI method, quite a few metabolites, such as terpenoids, flavonoids, glycosides, alkylphenols, amino acids, phenolic acids, tannins, and lipids, in fresh sage leaves, ginkgo leaves, and tea leaves were well detected and imaged by imprint DESI/PI. More than 80 metabolites were additionally identified, and more than 1 order of magnitude higher signal intensities were obtained for most metabolites in the negative ion mode. By virtue of the significant improvement of coverage and sensitivity of PI, the catechin biosynthesis network in fresh tea leaves could be clearly illustrated, indicating the potential applicability of imprint DESI/PI in exploring the sites and pathways of plant metabolic conversion.