Vinyl polymers incorporating a crowned spirobenzopyran moiety at the side chain were synthesized, and their alkali metal-ion complexation, photochromism, and photoresponsive ion-conducting behaviors were studied in comparison with similar polymers incorporating crown ether and spirobenzopyran moieties independently. The metal-ion complexation by their crown ether moiety significantly affected the photochromism of their spirobenzopyran moiety. The crowned spirobenzopyran polymers are similar to their corresponding monomeric analogue in their metal-ion complexing property and photochromism, with some difference induced by polymer effect. Almost no significant aggregation of the photoinduced merocyanine moiety was found in the crowned spirobenzopyran polymer, unlike the polymers carrying spirobenzopyran and crown ether moiety independently. The crowned spirobenzopyran polymers were applied successfully as components of photoresponsive ion-conducting materials.