We describe here the highly fluorescent self-assembled spherical aggregates of an azobenzene molecule without a specific ionic component in organic solution under UV light illumination. The first stage of trans-to-cis photoisomerization by UV light at 365 nm was followed by a significant enhancement, up to about 1000 times, of the emission from an azobenzene molecule (CN2Azo) with a long alkyl chain, which is due to the spontaneous formation of spherical organic aggregates. Fluorescence emission was further enhanced in the dark, and the quantum yield increased to about 0.3. We also report the significant size and structural changes of the aggregates, from nanometer-scale micelle-like aggregates to micrometerscale vesicular aggregates, obtained only from the variation in the concentration of an azobenzene derivative. The light-driven azobenzene aggregates show the size and structure dependences of emission wavelength from violet-blue to green-yellow.