The nitrile moiety, a cornerstone of modern organic chemistry and material science, is integral to natural products, pharmaceuticals and synthetic intermediates due to its exceptional versatility and reactivity. It serves as a key synthetic handle for transformations into carboxylic acids, amines, and aldehydes, while also enhancing reactivity at neighboring sites of molecules. The hydrocyanation of readily available alkynes represents a straightforward and atom-economic approach for nitrile synthesis (Figure ). Conventionally, this reaction relies on transition metal (TM) based catalysts, as TM-free hydrocyanation is typically restricted to activated alkynes. In recent years, developing new strategies for alkyne hydrocyanation has attracted considerable attention, including methods employing HCN surrogates as a substitute for the highly toxic and volatile HCN. However, a critical challenge that still remains underdeveloped is the control of regioselectivity in the HCN addition. Typically, asymmetrical, unbiased alkynes lead to a mixture of regioisomers which are difficult to separate due to their similar physicochemical properties (e.g., boiling points and retention times). Since only one isomer corresponds to the desired product, this not only reduces the atom economy, but it also significantly raises the costs of product isolation. Challenges in achieving regioselectivity in hydrocyanation have prompted most studies to focus on biased or symmetrical alkynes, with some reporting the formation of regioisomeric mixtures. Although Ritter et al. and Liu et al. have reported scarce examples of selective methods, these studies have been demonstrated exclusively for terminal alkynes (Figure ). In turn, reports of regioselective HCN addition to internal alkynes are limited to the electronically or sterically biased substrates, inherently predisposed to promote the formation of one regioisomer in excess. For instance, Fang et al. recently developed Pd-catalyzed protocols for alkynes conjugated with amide and ester groups, achieving excellent regioselectivity and stereoselectivity (Figure ). However, these methods were not demonstrated with electronically unactivated substrates, limiting their utility in broader synthetic contexts. To the best of our knowledge, no general strategy affords regioselectivity control of hydrocyanation of internal unbiased alkynes. Furthermore, relying on expensive and toxic TM-complexes has a substantial environmental impact. The removal of TM traces is particularly critical when products are intended for pharmaceutical applications. These limitations motivated us to explore a novel, regioselective, TM-free approach to unlock the potential of hydrocyanation methodology.