We report on the synthesis and characterization of a series of amphiphilic linear-dendritic block copolymers (LDBCs) as well as their self-assembly in water. The LDBCs are composed of a 2000 g/mol poly(ethylene glycol) (PEG) linear segment linked to the fourth generation of a 2,2-di(hydroxymethyl)propionic acid (bis-MPA)-based dendron containing 4-isobutyloxyazobenzene units (AZO) and hydrocarbon chains (C18) randomly connected to the periphery of the dendron. TEM and cryo-TEM images show that all the LDBCs form stable vesicles in water. The influence of AZO/C18 ratio in the photoresponse of the self-assemblies has been assessed as well as the encapsulation of both hydrophilic (Rhodamine B) and hydrophobic (Nile Red) fluorescent probes and the use of light as an external stimulus to trigger the release of the probes. The results show that by diluting the azobenzene content at the periphery of the dendron, the trans-to-cis photoisomerization rate can be substantially accelerated and the light-induced release activity can be tuned being the vesicles with a 50/50 AZO/C18 ratio the ones suffering the most significant changes upon irradiation.