Considering the previously reported Ni-based methodologies and our preliminary studies, we found that the Ni(COD)2/Xantphos system exhibits activity in HCN transfer to internal alkynes at 40 o C in toluene (for details see Supporting Informations). As may be expected, the TM-catalyzed hydrocyanation of internal unbiased alkyne 1a afforded a mixture of regioisomers 3a and 3a' with a ratio 38 : 62, unraveling a lack of regioselectivity control (Figure ). Noteworthy, this protocol requires strictly inert conditions and results in a mixture of products with similar properties that are challenging to separate using standard techniques such as column chromatography. Conversely, our TM-free method leads to 3a without any detectable traces of 3a', and even has a better total yield (83 % vs. 56%). Regarding the costs of TM complexes and prerequisite ligands, even for non-precious nickel complexes, our methodology results in a remarkable 2500-fold cost reduction for the synthesis of 3a. Overall, this method demonstrates superiority in regioselectivity, robustness, cost-efficiency, and sustainability when compared to the TM-based alternative protocol.