An ambient pressure ionization mass spectrometric strategy called internal extractive electrospray ionization mass spectrometry (iEESI-MS) has been developed and applied for direct profiling of labile phytochemicals inherent in various native plant tissues, including leaves, roots, and fruits. By passing the electrospray solvent through the plant tissue, a variety of phytochemicals, such as amino acids, sugars (e.g., glucose, sucrose, polysaccharides, etc.), and alkaloids, were continuously extracted from the sample interior, driven toward the natural/cut electro-spraying tip, and vaporized into gaseous ions for mass spectrometric interrogation. Phytochemical patterns obtained by iEESI-MS permit a rapid differentiation between various species of ginkgo plant and strawberry maturity stages, as well as characterization of physiological/pathologic conditions of chlorophytum comosum. Our experimental results further demonstrate that the established iEESI-MS approach is potentially useful for direct phytochemomics studies with minimal biodegradation, allowing elucidation of plant metabolism with high speed, specificity, and simplicity of analysis.