In the absence of directing auxiliaries, catalytic addition of nucleophiles to unactivated alkynes with accurate control of regioselectivity remains an ongoing challenge in organic chemistry. Herein, we realized a Ag-catalysed regiospecific hydration process of unactivated al-kynes. Computational investigations offered insights into the origin of the regiochemical outcome. The practicability and efficacy of the protocol was exemplified by its simple reaction conditions without incorporation of acidic additives, as well as the tolerance of a wide range of alkynes equipped with various functional groups, leading to the ketone products in up to 98% yield. Direct modification of bioac-tive organic molecules and gram-scale experiments further showcased the application potential of the strategy. The catalyst control prin-ciples are expected to advance efforts towards the development of general site-selective addition of nucleophile to unsaturated sub-strates, removing the requirement for neighboring activating groups.