Organic anions possess various functional properties; however, their presence in wastewater causes environmental pollution. Thus, coupling the separation of such species with the resultant function could be highly desirable. Herein, we propose a "killing two birds with one stone" strategy for highly efficient separation of organic pollutant anions from water at room temperature through direct construction of functional cationic metal-organic frameworks (CMOFs) based on the organic anions as charge-balancing anions. To illustrate this strategy, 2,4,6-trinitrophenolate anion (PA-) is chosen as a typical anion, while 4,4'-azo-triazole (atrz) is strategically chosen as a suitable neutral ligand. The resultant positive framework exhibits a high adsorption capacity and selectivity for PA-. Remarkably, its adsorption capacity is 869.6 mg g-1, which is more than 30 times that of multiwalled carbon nanotubes and 15 times that of activated carbon. Its capacity is even higher than that of BUT-13 (865 mg g-1), the highest adsorbent ever known. 1H NMR and single-crystal X-ray diffraction show that the high capacity is attributed to strong electrostatic interaction between the positive framework and PA-, which leads to all the pores being completely occupied by PA- anions. 1H NMR titration reveals that the selectivity comes from stronger hydrogen-bonding interaction between the ligand of the positive framework and PA-, which is confirmed from the eight times length of the shifted signal of atrz due to the addition of PA- compared with the competing anions. The stronger interaction is further confirmed from the high stability of the resultant CMOF in high-concentration salt solutions containing the competing anions, particularly in 100-fold molar NaNO3 and Na2SO4 solutions. Meanwhile, first-principles simulation shows that the high binding energy between the positive framework and PA- contributes to enhancing the selectivity. Moreover, the resultant CMOF is a potential energetic material with an improved oxygen balance, high heat of formation, and heat of detonation.