1, 4, 5, 8‐naphthalene diimide (NDI)‐based MOFs, due to their tunable structures and properties, have shown promising applications in photochromism, photocatalysis, electrocatalysis, photothermal therapy, etc. Herein, using an L‐alanine modified NDI ligand, i.e. N, N′‐bis(L‐alanine)naphthalenediimide (AlaNDI), a novel Cd‐NDI Cd (AlaNDI)(H2O)]·DMF·H2O (complex 1) was constructed under solvothermal conditions, which has an obvious different structure with the previously reported ones. Structural analysis shows that the packing structure of complex 1 consists of two adjacent Cd atoms sharing two AlaNDI ligands, forming a dimetallic building block [Cd2O8]. Each building block connects a total of four AlaNDI ligands, where two Cd atoms are bridged by two ligands. The building blocks are interconnected by ligands to form a two‐dimensional layered structure. Based on the features of the NDI skeleton, it was found that complex 1 possesses multiple stimulus responses involving sensitivity to light: a reversible photochromism property and good photocatalytic degradation activity against various dyes, especially against cationic dyes crystal violet (CV), methyl violet (MV), and Janus green B (JGB). In addition, the stimulus‐response mechanism was investigated by control experiments. It is revealed that the photocatalytic active species may be related to h+ and •OH.