Cis-to-trans transition of azobenzene compounds usually occurs under appropriate light irradiation or slow thermal relaxation, and one can hardly obtain complete cis-to-trans transition of azos due to the overlap of the n-π* transition of the trans and the cis isomers. We show that by viewing the photostationary state as a chemical equilibrium between the cis and trans isomers, triggered self-assembly of the trans isomers can promote the cis-to-trans transition, and trans azos with spectrum-grade purity can even be achieved using an elegantly designed coordinating azo. This work establishes a new paradigm for manipulating the cis-to-trans transition of azo compounds, which may inspire designs for various azo-based advanced materials.