In this paper, we describe the use of block copolymer micelles to incorporate Azo-AOT, an azobenzene-containing amphiphile having a structure suitable for reverse micelle formation and the fabrication of polyelectrolyte/micelle multilayer films. Interestingly, it is found that the PS21-PAA(157) micelles can incorporate more Azo-AOT molecules than the PS115-PAA(15) micelles, which is different from the case of incorporation of noncharged hydrophobic molecules. Moreover, Azo-AOT incorporated into the PS21-PAA(157) micelles undergoes a faster photoisomerization than in the PS115-PAA(15) micelles, which seems to be related to different aggregation states of Azo-AOT in the two micelles. From the data of UV-vis spectra, we can infer that Azo-AOT adopts a reverse micelle-like aggregation state in the PS115-PAA(15) micelles and disperses in the interface between the core and corona of PS21-PAA(157) micelles. These polyelectrolyte/micelle films incorporating functional amphiphiles have great potential in the field of functional thin films.