Matrix-assisted laser desorption/ionization Fourier transform mass spectrometry (MALDI/FTMS), operating in the negative ion mode, is used to directly observe sugar alcohol borate complexes in a number of plant fractions. The method involves virtually no sample workup and, in the case of celery phloem sap, requires only 40 nL of sap to observe the borate complex. The isolation and characterization of such soluble borate complexes is important in understanding the distribution of boron in plants. The results show that the complexes are composed of two mannitol or sorbitol ligands (L) complexed to a single borate center (B). In some cases, the boron is complexed to non-alditol monosaccharides. Sustained off-resonance collision irradiation dissociation of the BL2- complex, where L is a mannitol, gives fragments that confirm the proposed structure. Complexes of larger oligosaccharides have also been successfully observed using MALDI/FTMS. Semiempirical molecular orbital calculations (AM1) of the mannitol BL2- complex show that the most favorable configuration is with carbons 3 and 4 of both mannitol residues complexed to the borate. This allows maximum interaction of the remaining hydroxyls with the borate center.