Active water fracturing is one of the commonly used technologies in area for enhanced coalbed methane (CBM) extraction. However, after the fracturing process, active water residues may block the pore of coal and ultimately reduce the production of CBM. To address this limitation, pore structures of Dongtan (DT) and Houwenjialiang (HW) coal samples were subjected to active water fracturing effect using active water with different concentrations of PAM prepared using polyacrylamide (PAM). Methane adsorption experiment was conducted to probe the effect of active water on the adsorption of methane in coal samples. Additionally, low-temperature nitrogen-adsorption experiments (LT-NAT) and nuclear magnetic resonance (NMR) were probed to characterize the discrepancies in the pore structure and chemical composition surface functional groups of the two coal-sample types. The results showed that considerable discrepancies existed in the pore structures of the two coal-sample types; however, their surface functional groups were similar. The active water treatment had contrasting effects on the adsorption behavior of methane features of the two coal-sample types, that is, as concentration of PAM in the active water increased, the methane adsorption of the treated HW coal sample increased whereas that of the treated DT coal sample gradually decreased. The PAM molecules in the active water residue could adsorb methane, and blockage of pores by the residue will reduce the amount of methane adsorption. The combined effect of the two dominated the influence of active water fracturing on methane sorption. Further optimizing the active water formulation to improve the flowback effect can be a very useful channel of reducing damage to the coal seam.