Non-viral gene delivery has been a goal in the field of bionanotechnology for many years. Despite some remarkable successes in this area, however, transfection efficiencies still generally remain below those of the viral vector counterparts. While viruses directly inject DNA into cells in a state more readily accessible to the nucleus, non-viral vectors by necessity must form rigid complexes with DNA that, once entered into the cell, often slowly unpack preventing subsequent nuclear uptake and expression. Thus, the development of vectors with programmable release is highly desired. For this purpose we have developed 100-nm photoresponsive catanionic vesicles capable of inducing photoreversible coil-to-globule DNA transitions. The catanionic vesicles are formed from photosurfactants that can be “switched” from the active (visible light) to the passive (UV light) state. Thus, under visible light vesicles form spontaneously resulting in DNA compaction, while UV illumination causes vesicle rupture returning DNA to the expanded state. This photocontrol is used to release DNA from the carrier following cellular uptake, thus, enhancing nuclear uptake and gene expression.