Au nanocluster (AuNCs)-based luminescent functional materials have attracted the interest of researchers owing to their small size, tractable surface modification, phosphorescence lifetime and biocompatibility. However, the poor luminescence quantum yield (QY) of AuNCs limits their practical applications. Herein, we synthesized a type of AuNCs modified by 4,6-diamino-2-mercaptopyrimidine hydrate (DPT-AuNCs). Furthermore, organic acids, i.e., citric acid (CA) and tartaric acid (TA), were chosen for co-assembly with DPT-AuNCs to produce AuNCs-based luminescent materials with enhanced emission. Firstly, it was found that CA could significantly enhance the emission of DPT-AuNCs with the formation of red emission nanofibers (QY = 17.31%), which showed a potential for usage in I- detection. The n···π/π···π interaction between the CA and the DPT ligand was proposed as crucial for the emission. Moreover, chiral TA could not only improve the emission of DPT-AuNCs, but could also transfer its chirality to DPT-AuNCs and induce the formation of circularly polarized luminescence (CPL)-active nanofibers. It was demonstrated that the CPL signal could increase 4.6-fold in a ternary CA/TA/DPT-AuNCs co-assembly system. This work provides a convenient way to build AuNCs-based luminescent materials as probes, and opens a new avenue for building CPL-active materials by achiral NCs through a co-assembly strategy.