In this paper we describe the preparation of disulfide crosslinked polyglycerol hydrogels by the ring-opening crosslinking polymerization of glycerol and polyethylene glycol-based polyepoxides and Na2S2. Multivalent polyglycerol hydrogels were prepared by acid-catalyzed hydrolysis of remaining epoxide functionalities. Additionally, a near infrared fluorescent dye was encapsulated in the hydrogel network. Our hydrogels show complete degradation in reducing environments and a controlled release of the fluorescence dye was observed. These hydrogels are interesting scaffolds for bioactive substances, which can be released, triggered by the hydrogel degradation.