A novel multifunctional star-shaped aza-BODIPY mesogen was synthesized by a click reaction. This star-shaped aza-BODIPY mesogen undergoes self-assembly into a hexagonal columnar phase in its bulk state and spherical gels in organic solvents. Based on the investigation of the absorption and emission spectra and surface morphologies, J-aggregates are observed in their liquid crystalline (LC), gel and solid states, while H-aggregates are observed in n-hexane solution. Additionally, this star-shaped aza-BODIPY mesogen acts as a chemosensor toward CN⁻ ions via a nucleophilic addition reaction, and the corresponding addition product can yield white light emission (WLE) upon doping with blue dye. This star-shaped aza-BODIPY mesogen is represented as the first example of an aza-BODIPY derivative with LC, organogel and white light emission properties.