Self-Immolative Polymers (SIPs) are stimuli-responsive macromolecules which undergo a fast cascade depolymerization reaction in response to the stimulus. This unique behavior allows the elaboration of temporary structures with high potential of use as drug delivery vectors. In this work, SIPs sensitive to both UV and NIR light have been developed. Amphiphilic macromolecular architectures were designed in order to ensure the formation of self-assemblies. The triggered depolymerization of the structures were monitored by different methods, proving the on-demand and controlled kinetics. These SIP-based structures are likely to overcome important barriers encountered in the field of drug delivery, such as the passive release of the drugs, and to provide On/Off release profiles.