Large-scale volumetric fracturing is generally used during shale gas development. The return rate of fracturing fluid is low, and a large amount of slickwater is retained in the reservoir. The adsorption and desorption of partially hydrolyzed polyacrylamide (HPAM), an additive commonly used in slickwater, on the surface of shale was studied using Longmaxi shale from the Sichuan Basin. The experimental results showed that the mass ratio of the HPAM solution to shale reached saturation adsorption at 20:1 when the concentration of HPAM solution was 1000 mg/L and 25:1 when the concentration of HPAM solution was 500 mg/L. The mass ratio of the HPAM solution to shale was fixed at 25:1, and the adsorption equilibrium was reached at a HPAM concentration of 1000 mg/L when the aqueous solution temperature was 30 °C and 800 mg/L when the aqueous solution temperature was 60 °C. The Langmuir adsorption model yielded a better fit than the Freundlich adsorption model. The adsorption equilibrium time at 30 °C was at 60 min for a HPAM concentration of 500 mg/L, while for a concentration of 1000 mg/L, it was at 90 min. The adsorption equilibrium time at 60 °C was 40 min for a HPAM concentration of 500 mg/L, whereas it was 60 min for a HPAM concentration at 1000 mg/L. The pseudo-second order (PSO) kinetics model yielded better fits than the pseudo-first order (PFO) kinetics model. The adsorption of HPAM on shale was strong, and the adsorbed HPAM resembled cobwebs adhering to the shale surface. HPAM on the surface of shale after adsorption was able to resist the desorption capacity of water. However, when the amount of adsorbed HPAM on shale increased significantly, the amount of residual HPAM on the surface of the shale decreased rapidly during desorption in deionized water. The desorption of HPAM on the shale surface followed a modified desorption model. The higher the concentration of HPAM adsorbed on the shale surface was, the easier it was to desorb and the easier it was to be removed from the shale.