Amphiphilic Janus dendrimers containing first through third generation (G1-G3) photodegradable hydrophobic blocks were synthesized and their self-assembly in water was studied. While the G1 and G2 systems formed solid aggregates, the G3 system self-assembled to form dendrimersomes. These dendrimersomes were demonstrated to degrade upon irradiation with UV light, and exhibited triggered release of both hydrophobic and hydrophilic payloads.