A new class of neutral ligands is synthesized and studied for the binding properties with anions by electrochemical methods. The binding of calix[4]diquinone 1 with HSO4 causes a large negative shift of the electrode potentials of the calix[4]diquinone. This novel neutral anion receptor 1 binds anions through hydrogen-bonding and shows high selectivity for HSO4 over H2PO4, Cl and CH3CO2. The selectivity of HSO4, over H2PO4, Cl, and CH3CO2 may be attributed to the stronger hydrogen-bonding with the urea moiety, and also with the quinone moiety of 1 receptor, and also the greater compatibility of the cavity of 1 with tetrahedral HSO4.