Herein, we report for the first time a highly emissive higher-order assembled structure of BSA-Au NCs in the presence of cucurbit[7]uril, which enhances the absolute fluorescence quantum yield of BSA-Au NCs up to 40%. Cucurbit[7]uril neutralizes the surface charge of BSA-Au NCs, and hence aggregation happens. This aggregation shows reversible disaggregation in the presence of adamantylamine.