Herein, we report a green, sustainable, and metal‐free, one‐pot three‐component protocol for the synthesis of indeno [1, 2‐b] quinoxalin‐11‐ylidenamine derivatives using a novel, effective, and recyclable mesoporous heterogeneous organocatalyst [MTP−IL]. [MTP−IL] was constructed by immobilizing an imidazolium‐cation‐based ionic liquid on a melamine−terephthalaldehyde covalent organic polymer and was thoroughly characterized using several analytical techniques. It displayed high thermochemical stability and catalytic efficacy, offering title compounds with 90–94 % yields in a short reaction time, and was recyclable for up to six cycles. The synthesized compounds were characterized through FTIR, 1H, and 13C Nuclear Magnetic Resonance (NMR), and the molecular structure of N′‐(11H‐indeno[1,2‐b]quinoxalin‐11‐ylidene)benzohydrazide (7) was confirmed by the Single Crystal XRD (SCXRD) analysis. The key features of the present protocol are the use of ethanol as a green solvent, easy catalyst recovery, a simple work‐up procedure, and zero involvement of any metal.