Abstract: In order to improve the adsorption capacity of microporous molecular adsorption coatings, an ultra-low concentration methanol ammonium fluoride solution was utilized to etch zeolite 5A to enhance its specific surface area and micropore volume. A high specific surface area zeolite 5A molecular adsorption thermal control coating was then prepared by spraying process. The test results showed that after being etched with 0.01wt% methanol ammonium fluoride solution, the specific surface area of zeolite 5A increased from 603.671 7 m²·g^-1 to 703.088 8 m²·g^-1, and the total micropore volume increased from 0.225 6 cm³·g^-1 to 0.270 2 cm³·g^-1. The adsorption capacity of the prepared coating increased from 2.092 2 mg·cm^-2 to 2.438 2 mg·cm^-2. These coatings’ thermal control performance and high/low temperature cycling stability both met the technical requirements for spacecraft thermal control coatings in space. The proposed study may offer a reference for the development of high-performance space used molecular contamination adsorption materials.