A significant emission enhancement (>100-fold) of glutathione-capped bimetallic gold and copper nanoclusters (AuCuNC@GSH) was achieved by assembling with Al3+ ions and by assembly-induced emission enhancement (AIEE). Further chelation of myricetin to Al3+ resulted in emission quenching of AuCuNC-Al3+, which was applied to specifically detect myricetin. Two linear responses were shown in the range of 0–1.5 μM and 1.5–50 μM, separately, leading to a low limit of detection at 8.7 nM. The method was successfully and accurately applied to myricetin determination in grape juice, which showed good application for real samples. Finally, the in-depth mechanism revealed that both the chelation of myricetin and Al3+ and the inner filter effect (IFE) between myricetin-Al3+ and AuCuNC-Al3+ greatly contributed to the quenching response of myricetin. Therefore, the present study provides an easy way to improve the fluorescence property of metal nanoclusters. Additionally, it supplies a cost-effective and easily performed approach to detect myricetin with high selectivity and sensitivity.