Abstract: Liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC-ESI/MS/MS) in negative ion mode was used for the screening of bisbibenzyls in 2 bryophyte crude extracts (Marchantia polymorpha L. and Asterella angusta). To obtain the mass spectrometric characteristics of bisbibenzyls, 15 confirmed bisbibenzyl compounds were investigated， and the fragmentation patterns were proposed. Further characterization of each crude extract was performed using full scan and MS/MS product ion scan analysis. The confirmed or unconfirmed bisbibenzyls were identified or proposed by comparison of the retention behavior, mass spectrometric data and the UV spectroscopic data with confirmed bisbibenzyl compounds. As a result, 5/18, 8/16 confirmed/unconfirmed bisbibenzyls are determined in the two crude extracts respectively. The method is simple, reliable and sensitive, and it can be used for screening other bisbibenzyl analogs.