Metal catalysts supported by single-chain nanoparticles (SCNPs) can exhibit high efficiency and selectivity due to excellent dispersibility in solution and nanoconfinement effects. However, the contradiction between dispersibility and recyclability is a challenge. In present study, a SCNP-supported metal catalytic system inspired by worker bees returning to hives is proposed. SCNP catalysts are anchored onto the modified surface of silicate via a dynamic covalent bonding based-on Diels–Alder (DA) reaction. As the temperature increases (up to 120 °C), SCNPs release from the surface of silicate via reverse DA reaction to the reaction system of alkyne, and precisely catalyze the coupling reaction of phenylacetylene. Upon completing the catalytic process, SCNPs can return to the silicate surface via DA reaction during the cooling process. This catalytic system facilitates the efficient recovery and reuse of SCNPs catalysts by making maximal use of their efficiency and selectivity. Furthermore, this recyclable SCNP catalytic system has exceptional catalyst fatigue resistance, retaining over 90% catalytic conversion efficiency and outstanding selectivity after 20 cycles of release, catalysis, and recovery, which is comparable to their initial performance. In the future, this catalytic process and system can be expanded to include more catalysts and solid carriers, such as bulky, sheet, film, and microporous materials.