A novel class of macrobicyclic receptors for carbohydrate recognition based on upper rim, peptide-bridged calix[4]arenes has been designed and synthesized. Receptor 12, in which a charged phosphate group cooperates with peptide hydrogen-bonding donor and acceptor groups in the binding process, is the most efficient and selective in the complexation of simple carbohydrate derivatives. The selectivity observed is toward beta-glucoside 13a, which is better bound (DeltaG degrees = 19.6 kJ mol(-)(1)) compared to the corresponding alpha anomer 13b (DeltaG degrees = 17.0 kJ mol(-)(1)) and to the beta-galactoside 13c (DeltaG degrees = 17.7 kJ mol(-)(1)) in CDCl(3). A substantial drop in the stability constant is observed by esterification of the phosphate group in the host 12 or by alkylation of the OH groups in the 2 and 3 positions in the beta-glucoside and beta-galactoside derivatives. On the basis of a careful analysis of the (1)H NMR data available, a binding mode of the beta-octylglucoside 13a to receptor 12 is proposed.