The stable geometries of fucose-benzene complex and the stabilization energies by formation of the complex (E(form)) were studied by ab initio molecular orbital calculations. The benzene ring has close contact with an O-H or C-H bond of fucose in the optimized geometries (OH/pi hydrogen-bonded structures and CH/pi contact structures). The E(form) calculated for the most stable OH/pi hydrogen-bonded structure was -5.1 kcal/mol. The E(form) calculated for the most stable CH/pi contact structure was -4.5 kcal/mol, which shows that significant attraction exists between the nonpolar surface of fucose and a benzene. The E(form) is close to the interaction energies in typical hydrogen-bonded complexes. A few nearly isoenergetic CH/pi contact structures were found by the calculations, which suggests that the directionality of the carbohydrate-aromatic interaction is weak. The dispersion interaction is the major source of the attraction in the complex. The electrostatic contributions to the attraction are relatively small. Although the size of the interaction energy is not largely different from that of typical hydrogen bonds, the nature of the carbohydrate-aromatic interaction, which is sometimes denoted as a CH/pi hydrogen bond, is completely different from that of typical hydrogen bonds, which have strong directionality due to the strong electrostatic interactions.