The acid-base properties of nanoscopic water confined in the black soap films (BSFs), which were prepared from aqueous solutions of sodium dodecylsulphate (SDS) with the dye neutral red (NR) as a pH probe, were investigated using a combination of UV-vis and FTIR spectroscopy. For the SIDS micellar solutions at pH 1.0-9.5 adjusted with HCl/NaOH solutions and at pH 9.4 with ammonium buffered solution, the aqueous core thicknesses in the corresponding BSFs ranged from 2.7 to 6.2 nm, and the nanoscopically confined water exhibits unusual buffer action resistant not only to acidic/alkaline solutions but also to standard buffer solution. In the heavily water-depleted confined zones, it is most likely that charge pairs in proton-transfer reactions could not be formed effectively and proton transfer was prohibited in the absence of sufficient solvating ability. Theoretical analyzes indicated that the buffer action of the nanoscopic water originated from the confinement effect of two charged surfaces of the BSFs. These results might inspire deeper understanding and further studies of biobuffering, enzyme superactivity, acid-catalyzed reactions, and Nafion fuel cell membranes. (C) 2009 Elsevier Inc. All rights reserved.