A method based on extractive electrospray ionization mass spectrometry (EESI-MS) was developed to obtain the mass spectra of three types of soil samples with minimal sample pre-treatment. EESI could tolerate the complex matrices of soil sample solutions and readily generate mass spectra without sample cleaning. The mass spectra clearly demonstrated the differences of organics among three types of soil samples. Dehydroabietic acid and the combination of syringaldehyde and pinoresinol were detected in extracts of Pinus massoniana and Schima superba Gardn et. Champ. respectively by extractive electrosprary ionization tandem mass spectrometry (EESI-MS/MS).