Incorporating metal clusters into the confined cavities of metal−organic frameworks (MOFs) to form MOF-supported catalysts has attracted considerable research interest with regard to carbonylation reactions. Herein, a self-templating method is used to prepare the zinc oxide (ZnO)-supported core–shell catalyst ZnO@Pd/ZIF-8. This facile strategy controls the growth of metal sources on the ZIF-8 shell layer and avoids the metal diffusion or aggregation problems of the conventional synthesis method. The characteristics of the catalysts show that the palladium (Pd) clusters are highly dispersed with an average particle size of ≈1.2 nm, making them excellent candidates as a catalyst for carbonylation under mild conditions. The optimal catalyst (1.25-ZnO@Pd/ZIF-8) exhibits excellent activity in synthesizing α, β-alkynyl ketones under 1 atm of carbon monooxide (CO), and the conversion rate of 1, 3-diphenylprop-2-yn-1-one is 3.09 and 3.87 times more than those of Pd/ZIF-8 and Pd²⁺, respectively, for the first 2 h. Moreover, the 1.25-ZnO@Pd/ZIF-8 is recyclable, showing negligible metal leaching, and, under the conditions used in this investigation, can be reused at least five times without considerable loss in its catalytic efficiency. This protocol can also be applied with other nucleophile reagents to synthesize esters, amides, and acid products.