A series of novel azobenzene-based amphiphilic random copolymers P(POSSMA-co-AZOMA-co-DMAEMA) were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. A light and reduction dual-responsive azo group, pH-responsive tertiary amine group and super hydrophobic POSS moiety were incorporated into the polymer chain to generate multi-stimuli-responsiveness. Self-assembly of these amphiphilic copolymers led to the formation of spherical micelles in aqueous solution. The light, pH and reduction responsive properties of the micelles were investigated systematically by DLS, TEM, UV-vis, FTIR and NMR. The azo groups can undergo trans–cis isomerization under UV light irradiation, thus causing a diameter change of the micelles. Owing to the large proportion of tertiary amine groups in amphiphiles, these micelles showed sensitive pH-response behavior. The hydrophobic azo pendant in the polymer chain completely reduced to a more hydrophilic substituted aniline in a reductive environment, resulting in the increase of overall hydrophilicity of amphiphiles and the disassembly of polymeric micelles. Owing to these multi-stimuli–responses, the polymeric micelles showed rapid and efficient release properties of hydrophobic molecules in response to pH and reductive stimuli.