Energetic hydrogen-bonded organic frameworks (E-HOFs), as a type of energetic material, spark fresh vitality to the creation of high energy density materials (HEDMs). However, E-HOFs containing cations and anions face challenges such as reduced energy density due to the inclusion of crystal water. In this work, the modification of amino groups in N-rich organic units could form a smart building block of hydrogen-bonded frameworks capable of changing the volume of the void space in the molecule through adaptive deformation of E-MOF blocks, thus enabling the replacement of water. Based on the above strategy, we report an interesting example of a series of hydrogen-bonded organic frameworks (E-HOF 2a and 3a ) synthesized using a facile method. The crystal structure data of all of the compounds were also obtained in this work. Anhydrous 2a and 3a exhibit higher density, good thermal stability, and low mechanical sensitivity. The strategy of covalent bond modification for the host molecules of energetic frameworks shows enormous potential in eliminating the crystalline H 2 O of hydration and exploring high energy density materials.