Magnetic responsive ionic liquid (MIL) demonstrated an advanced photomobility in confined narrow spaces through the doping of photoresponsive azobenzene by the interplay of supramolecular π-cations. Moreover, reversible physisorption/desorption of CO2 was achieved based on the photocontrolled solid-liquid transitions of the mixtures. Our approach opens opportunities to obtain multi-stimuli response through the coordinated supramolecular interplay of each responsive component.