We report the design and synthesis of the first aliphatic covalent organic framework (COF), NUS-119, and its subsequent conversion to NUS-120, marking the first fully saturated COF. NUS-119 is built by imine-linkages exhibiting high crystallinity and porosity, achieved by using a Lewis acid as a reaction modulator to circumvent compatibility issues between the Brønsted acid and the strong basic monomer. The structure was successfully solved using 3D microelectron diffraction (microED) techniques. NUS-119 and NUS-120 demonstrated remarkable catalytic performance in base-catalyzed Knoevenagel condensation reactions, exhibiting high conversion rates, excellent size selectivity, and good recyclability. This work advances the understanding of COF materials and paves the way for future research and applications.