With increasing demands for more rapid and practical analyses, various techniques of ambient ionization mass spectrometry have gained interest due to its speed of analysis and the abundance of information provided. Herein, an ambient ionization technique that utilizes corona discharge was applied, for the first time, to analyze whole seeds of black and white peppers. This setup requires no solvent application or gas flow, thus resulting in a very simple and rapid analysis that can be applied directly to the sample without any prior workup or preparation. Combined with robust data pre-processing and subsequent chemometric analyses, this analytical method was capable of indicating the geographical origin of each pepper source with up to 98% accuracies in all sub-studies. The simplicity and speed of this approach open up the exciting opportunity for onsite analysis without the need for a highly trained operator. Furthermore, this methodology can be applied to a variety of spices and herbs, whose geographical indication or similar intellectual properties are economically important, hence it is capable of creating tremendous impact in food and agricultural industries.