Inspired by the role of multicatalysis in enabling new reactivity by activating the inherently unreactive sites of molecules, herein, we present a dual-catalytic strategy for the TM-free hydrocyanation of unbiased internal alkynes (Scheme 1c). This method achieves exclusive regioselectivity, mild conditions and broad scope, with high atom economy and reduced costs compared to TM-based approaches. Furthermore, this study not only addresses critical challenges in the hydrocyanation reaction but also demonstrates the potential of TM-free multicatalytic systems for developing previously unattainable, selective, and sustainable hydrofunctionalizations.