Stimuli responsive drug carrier systems have emerged as important devices in the field of biomedical applications and targeted drug delivery. General challenges for controlled release of drugs are timed or prolonged release, targeted or local release, and overcoming physicochemical barriers in the body. In order to release the cargo a phase transition or macroscopic change of the hydrogel network has to be triggered. Several triggers have been successfully applied, such as: pH, ionic strength, mechanical stress, redox potential and light. Light is of particular interest since it is spatio-temporally controlled and can be harmless when clinically applied, depending on wavelength and intensity. However, human tissue limits the use of light as the penetration depth is just a few centimetres depending on the applied wavelength, which inherently limits the use of external light sources for triggered release. To overcome these limitations, we were excited to investigate the potential of in situ generated light, known as Cerenkov luminescence (CL), and employ it as a drug release trigger. CL is generated when a charged particle, generated by the decay of radionuclides or external radiation, travels faster than the speed of light in a dielectric medium such as water or tissue. CL has a broad emission spectrum with a maximum emission around 380 nm (UV-A), and is usually generated with low intensity. CL has been employed as a light source in anticancer therapies, where nanoparticles passively target solid tumours and generate reactive oxygen species (ROS). Moreover, CL is found an effective trigger for decaging doxorubicin and is employed to generate reactive singlet nitrene species, that subsequently react with extracellular proteins or lipids and 'tag' solid tumours with a drug or dye. For future application with CL triggers, we aimed at developing hydrogels with light sensitive groups with an absorption maximum in the Cerenkov emission window and high quantum yield of photodegradation.