Photoresponsive molecules with more than two intrinsic stationary states are very Interesting. Here, we demonstrate a series of crown ether (CE) substituted donor-acceptor Stenhouse adducts (DASAs) that can be switched between three stationary states under orthogonal control of light and metal ions. DASA-CE molecules are self-assembled into 1:1 head-to-tail supramolecular structures to form di-linear states due to strong van der Waals interactions between electron-donating and -withdrawing moieties. Furthermore, treatment with metal ions (Na+ or K+) switches the di-linear back to the linear state, which is reversible after adding free crown ether. On the other hand, green light irradiation induces linear-to-cyclic isomerization of DASA-CE, while the photoisomerization from di-linear to cyclic state is inhibited. The reverse cyclic-to-linear isomerization can occur under heating in the dark. All in all, the orthogonal switching of DASA-CE between di-linear, linear and cyclic states enables the development of smart materials in environments with complex stimuli.