This study demonstrated a facile ionization method with the use of real samples for the ionization of their main compositions at ambient conditions for mass spectrometric analysis. Analyte ions derived from the real samples were readily observed in the mass spectrum when placing the samples close (≤1 mm) to the inlet of the mass spectrometer applied with a high voltage. No additional accessories such as an ionization emitter, a plasma generator, or a high voltage power supply were required for this approach. Ionization of semivolatiles derived from the samples occurred between the samples and the inlet of the mass spectrometer presumably owing to the dielectric breakdown induced by the electric field provided by the mass spectrometer. Real samples including plants, medicine tablets, and gloves with contaminants were used as the model samples. The putative ionization mechanisms are also discussed in this study.