As one of the natural nucleobases, guanine has attracted increasing interest in molecular self-assembly science because of its abundant interaction sites and high electron cloud density. Guanines, guanine derivatives, and guanine-rich DNA sequence are able to self-assemble into versatile aggregate structures by the means of hydrogen bonds and π-π, ion-dipole, solvophobic, and electrostatic interactions. Recent advances have shown that many guanine analogue-based (G-based) luminescent aggregates exhibit promising applications for fluorescent and chemiluminescent sensing and circularly polarized luminescence (CPL). This perspective summarizes the state-of-art strategies for constructing G-based assemblies and presents representative examples for luminescence functions. Finally, the inspirations are provided for exploiting unique G-based systems and luminescent G-based assemblies.