A novel, highly efficient, and phosphine-free heterogeneous palladium-MOF catalytic system for the carbonylative Sonogashira coupling of terminal alkynes with aryl iodides was developed. The catalyst could efficiently promote the carbonylative coupling reaction under atmospheric pressure of CO, affording the corresponding aryl α,β-alkynyl ketones in good to excellent yields. Besides high activity and selectivity, the proposed catalytic system features a broad substrate scope for both alkynes and aryl iodides. Moreover, the heterogeneous catalyst was recyclable, showed negligible metal leaching, and could be reused at least five times without significant loss in catalytic efficiency under the investigated conditions.