Covalent organic frameworks (COFs) are a new class of porous crystalline materials fabricated by designed synthesis to have high surface area, very low densities, and tunable pore dimensions for use in gas storage, catalysis, and opto-A C H T U N G T R E N N U N G electronics. [1] The formation of covalent bonds involved in connecting molecular building blocks during polymerization processes can retard crystalline network formation, however, COFs based on BÀO, [2] CÀN, [3] and BÀN [4] bonds have been reported. The initial design of COFs was directed toward gas storage applications because of their inherent low density (i.e., made of H, C, N, B, O, Si) and high surface area, which can mitigate gravimetric and volumetric constrains for the onboard storage of hydrogen and methane. [5] Although COFs derived from B À O bond formation have been widely investigated, their low chemical stability leads to rapid decomposition upon exposure to moisture and limits their effective use in gas storage under practical conditions. This drawback has been addressed in new COF materials constructed through the formation of C À N bonds and found to have enhanced chemical robustness. To date, C À N-linked COFs, such as triazine-, imine-, and hydrazone-linked COFs, typically possess moderate specific surface areas that can hinder their application in gas storage. Moreover, recent studies on a variety of porous materials, such as COFs, metal-organic frameworks (MOFs), [6] porous organic polymers, [7] etc., have correlated high surface area to enhanced gas storage capacity especially under high pressure conditions. One of the effective methods for attaining high porosity in organic materials has been the use of rigid or expanded 3D building units, [8] however, extrapolating this approach to imine-linked COFs resulted in framework interpenetration and only moderate surface area for the 3D COF-300 (SA BET = 1360 m 2 g À1 ). [3b] Likewise, the use of p-electron rich building units has afforded low surface area for the 2D COF-66 (SA BET = 360 m 2 g À1 ) [9] and, to the best of our knowledge, the use of imine-linked COFs in gas storage has been only investigated theoretically. [10] [a] Dr.