To study the adsorption performance of coal bodies after alkaline solution erosion and the microscopic mechanism of alkali erosion on coal bodies, isothermal adsorption experiments at different pH values and with different numbers of soaking days were conducted on high-order coal bodies from the Chengzhuang mine. The results showed that the adsorption capacity of the coal bodies after alkali leaching was improved compared to that of the original coal, all of which was in accordance with the Langmuir equation. The unit adsorption capacity of coal samples increased gradually with an increase in the number of soaking days and solution pH, reaching the maximum at pH 13 and eight soaking days. The adsorption constant a of the coal sample was positively correlated with the pH, and the number of soaking days was a power exponential function; the adsorption constant b increased gradually with an increase in the pH of the solution and increased first and then decreased with an increase in the number of soaking days. The change in the adsorption of coal samples occurs because the alkaline solution reacts with the minerals in the coal as well as the mineral ions, and the resulting complex gels and precipitates block the pore channels of the coal body, which in turn inhibits the adsorption of gases. The presence of Na, Mg, Al, Si, Ca, Fe, and other elemental compounds detected in the generated sediments verified the mechanism of alkaline solution erosion. The changes in the microscopic pore structure of the coal body were quantified by low-temperature liquid nitrogen adsorption experiments. The small and medium pore volumes of the coal samples reached the maximum values at pH 13 and with eight soaking days, which is in agreement with the conclusion of optimal alkali modification.