We present a versatile and facile method to enhance user-control of small molecule drug release from a poly(ethylene glycol)-based hydrogel using the host/guest complex formed between an azobenzene derivative guest and a β-cyclodextrin host. A model drug is formed from a short peptide containing a fluorophore and an azobenzene functional group on one terminus. Upon irradiation with UV light, azobenzene isomerization leads to decreased complex formation and an on-demand acceleratation of the release rate of an entrapped model drug.