Alginate/Fe3+ hydrogels were fabricated on hyaluronic acid (HA) and poly(allylamine hydrochloride) (PAH) multilayers to yield photoresponsive nanometer-scale hydrogels. Light irradiation of the resulting hydrogels induced the photoreduction of "hard" Fe3+ to "soft" Fe2+ cations, leading to changes in the mechanical properties of the hydrogels related to their cross-linking behavior. The buildup and the phototriggered response of the supported alginate hydrogels were followed in situ with a quartz crystal microbalance (QCM) using an open cell allowing light irradiation from an LED source on top of the hydrogel. The results were correlated to the release profiles of folic acid, employed herein as a drug model, obtained from light-irradiated supported iron alginate hydrogels.