Constructing artificial helical structures through hierarchical self-assembly and exploring the underlying mechanism are important, and they help gain insight from the structures, processes, and functions from the biological helices and facilitate the development of material science and nanotechnology. Herein, the two enantiomers of chiral Au­(I) complexes ( S )-1 and ( R )-1 were synthesized, and they exhibited impressive spontaneous hierarchical self-assembly transitions from vesicles to helical fibers. An impressive chirality inversion and amplification was accompanied by the assembly transition, as elucidated by the results of in situ and time-dependent circular dichroism spectroscopy and scanning electron microscope imaging. The two enantiomers could serve as ideal chiral templates to co-assemble with other achiral luminogens to efficiently induce the resulting co-assembly systems to show circularly polarized luminescence (CPL). Our work has provided a simple but efficient way to explore the sophisticated self-assembly process and presented a facile and effective strategy to fabricate architectures with CPL properties.