The microscopic interaction mechanism between working fluids and shale reservoirs is the key basic issue for the efficient development of shale gas. The initial water saturation of clay-rich shale is low, and the water absorption through strong chemical osmosis is an important factor for the wellbore instability of the drilling fluid filtration loss and the low flowback rate of hydraulic fracturing. Membrane efficiency is a key parameter in evaluating the mechanical-chemical coupling of shale-fluid interaction. Because microcracks develop in reservoir shale, pressure transfer experiments are no longer capable of obtaining membrane efficiency value. In this paper, the characteristics of shale water saturation are considered. The model calculating membrane efficiency is obtained, and the shale membrane efficiency of the reservoir studied, based on the triple-layer model of clay mineral-water interface electrochemistry. Membrane efficiency of unsaturated shale depends on the excess charge density of the surface of the solid in different water saturations. The analysis of factors influencing shale membrane efficiency in unsaturated reservoirs shows that the shale membrane efficiency decreases with the increase of water saturation under unsaturated conditions. The partition coefficient of counterion in the Stern layer, cation exchange capacity, and solute concentration in pore fluid will affect the membrane efficiency of unsaturated shale. The membrane efficiency of the reservoir section shale in Fuling area is calculated and analyzed, and the water-absorbing capacity by chemical osmosis of the reservoir interval shale is evaluated based on the membrane efficiency model of unsaturated shale.