The classic Fokin mechanism of the CuAAC reaction of terminal alkynes using a variety of Cu(I) catalysts is wellknown to include alkyne deprotonation involving a bimetallic σ,π-alkynyl intermediate. In this study, we have designed a CNTsupported atomically precise nanocluster Au 4 Cu 4 (noted Au 4 Cu 4 /CNT) that heterogeneously catalyzes the CuAAC reaction of terminal alkynes without alkyne deprotonation to a σ,π-alkynyl intermediate. Therefore, three nanocluster−π-alkyne intermediates [Au 4 Cu 4 (π-CHC-p-C 6 H 4 R)], R = H, Cl, and CH 3 , have been captured and characterized by MALDI-MS. This Au 4 Cu 4 /CNT system efficiently catalyzed the CuAAC reaction of terminal alkynes, and internal alkynes also undergo this reaction. DFT results further confirmed that HCCPh was activated by π-complexation with Au 4 Cu 4 , unlike the classic dehydrogenation mechanism involving the bimetallic σ,π-alkynyl intermediate. On the other hand, a Cu 11 /CNT catalyst was shown to catalyze the reaction of terminal alkynes following the classic deprotonation mechanism, and both Au 11 /CNT and Cu 11 /CNT catalysts were inactive for the AAC reaction of internal alkynes under the same conditions, which shows the specificity of Au 4 Cu 4 involving synergy between Cu and Au in this precise nanocluster. This will offer important guidance for subsequent catalyst design.

Atom‐precise nanoclusters‐metal‐organic framework (APNC/MOF) composites, as bifunctional material with well‐defined structures, have attracted considerable attention in recent years. Despite the progress made to date, there is an urgent need to develop a generic and scalable approach for all APNCs. Herein, the authors present the Exploiting Fracture Strategy (EFS) and successfully construct a super‐stable bifunctional APNC/ZIF‐8(300 °C) composite overcoming the limitations of previous strategies in selecting APNCs. The EFS utilizes the fracture of ZnN in ZIF‐8 after annealing at 300 °C. This method is suitable for all kinds of S/P protected APNCs with different sizes, including uncharged clusters Au1Ag39, Ag40, negatively charged Au12Ag32, positively charged Ag46Au24, Au4Cu4 and P‐ligand‐protected Pd3Cl. Importantly, the generated APNC/MOF show significantly improved performances, for example, the activities of Au12Ag32/ZIF‐8(300°C), Au4Cu4/ZIF‐8(300°C), and Au1Ag39/ZIF‐8(300°C) in the corresponding reactions are higher than those of Au12Ag32, Au4Cu4, and Au1Ag39, respectively. In particular, Au12Ag32/ZIF‐8(300 °C) shows higher activity than Au12Ag32@ZIF‐8. Therefore, this work offers guidance for the design of bifunctional APNC/MOF composites with excellent optimization of properties and opens up new horizons for future related nanomaterial studies and nanocatalyst designs.