AbstractExcitonic 0D and 2D lead‐halide perovskites have been recently developed and investigated as new materials for light generation. Here broadband (>1 eV) emission from newly synthesized 0D lead‐free colloidal Cs3Bi2I9 nanocrystals (NCs) is reported. The nature of their emissive states as well as the relative dynamics which are currently hotly debated are investigated. In particular, it is found that the broadband emission is made by the coexistence of emissive excitons and sub‐bandgap emissive trap‐states. Remarkably, evidence of enhanced Raman scattering from the ligands is observed when attached to the NCs surface, an effect that is preliminarily attributed to strong exciton‐ligands electronic coupling in these systems.