Understanding water distribution behaviors plays an essential role in shale gas development due to the hydraulic fracturing technology. In this study, water vapor adsorption isotherms were measured for Upper Triassic Yanchang and Lower Silurian Longmaxi samples at 288.15 K, 298.15 K and 308.15 K to investigate the adsorption behaviors of water on shale. For a description of adsorption process, a Dent's model provides an estimate of primary and secondary adsorption sites of water adsorption. The effects of temperature, shale mineralogy, and water distribution were discussed. The results show that temperature has a negative effect on water vapor adsorption. Adsorption capacities of primary and secondary sites decrease with increasing temperature. Water vapor adsorption capacity is tightly associated with clay content, whereas water vapor adsorption has no significant relationship with total organic carbon (TOC). Normalized water vapor adsorption content also has no significant relationship with TOC, which indicates no obvious correlation between water vapor adsorption and TOC content. The inter-crystal pores of clay minerals provide significant specific surface for gas adsorption in shale. At low relative pressure, a large number of water molecules adsorb on the primary sites. At high relative vapor pressure, most of the primary sites have been occupied, so that the secondary adsorption sites will be utilized. Therefore, due to relative weak binding energies in secondary adsorption sites, water cluster are formed in micro-pores of shale. As relative vapor pressure increases, capillary condensation gradually predominates over the adsorption. The study will reveal mechanism of water adsorption and distribution characteristics on shale and provide some foundation for geological reserve estimation and shale gas recovery prediction.