A simple and efficient approach to endow the controllable multi-stimuli-responsive property for the supra molecular polymer was successfully developed by rationally introducing iodine into a novel naphthalimide-functionalized pillar[S]arene-based supramolecular polymer (PNA superset of GBP). Interestingly, by introducing iodine into the supramolecular polymer PNA superset of GBP, the iodine could not only control the optical properties and self-assembly states of PNA superset of GBP via electronic donor-acceptor effect but also control the molecular recognition properties by competitive redox reaction. Benefiting from these excellent iodine controlled multiresponse properties, the PNA superset of GBP showed selective fluorescent response for cyanide, cysteine, and mercury in supramolecular polymer gels, water solutions, and living cells with high sensitivities. The supramolecular polymer. PNA superset of GBP could act as a novel smart material for selective detection. CN-, Hg2+, and L-Cys.