Water vapor adsorption/desorption isotherms are measured on five shales from Illinois basin by dynamic vapor sorption method. The experimental adsorption data are modeled by the Guggenheim, Anderson, and De Boer model and the Freundlich model over the entire range of measured relative humidity (Rh) values (0–0.95). Modeling results show that shale hydration is controlled by surface chemistry at low Rh through a strong intermolecular bonding, while is mainly influenced by the pore structure at high Rh (>0.9) through capillary condensation. This is consistent with the progressive decrease of isosteric heat of adsorption with water content, obtained by the Clausius‐Clapeyron equation. Exceptionally, for the one shale containing 8.6% montmorillonite, mesopore condensation only accounts for 33% of the measured water adsorption even at Rh ~0.95 due to the limited external pores and the important role of clay swelling. The specific surface area defined by Guggenheim, Anderson, and De Boer analysis as available for water adsorption is larger than that available for low‐pressure N2 adsorption due to the complex surface chemistry. The one shale rich in expansive montmorillonite and with a large interlayer capacity for water but inaccessible to N2 molecules conditions this result. Among the other four shales, one with high kerogen content behaves the highest water adsorption, possibly due to the high content of oxygen‐containing functional groups and the potentially high pore volume of kerogen. These findings contribute to a better understanding of water storage and transport behavior in shales and impact behavior relevant to structures and reservoirs founded in such media.

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