Adsorption isotherms of water on porous carbons generally show large hysteresis loops whose origin is believed to be different from simple gases adsorption in mesoporous solids. In this paper, we discussed in details the behavior of water adsorption isotherms and their descending scanning curves for two carbons of different topologies, a highly graphitized thermal carbon black, Carbopack F, and a highly ordered mesoporous carbon, Hex. For both solids, very large hysteresis loops are observed, but their behaviors are different. For Carbopack F, the loop extends over a very wide range of pressure and the loop is larger when the descending is started from a higher loading; while for Hex, the hysteresis loop shows distinct steps, the number of which depends on the loading where the descending starts. By carefully analyzing the scanning curves from different loadings, we established the mechanism of water adsorption in Hex as a sequence of three steps: (1) water molecules adsorb on functional groups located at the junctions between adjacent basal planes of graphene layers, (2) growth of water clusters around the functional groups, and (3) bridging of adjacent clusters to form larger clusters, followed by a complete filling of mesopores. (C) 2015 Elsevier Ltd. All rights reserved.