A novel method for the synthesis of 1,2,3‐triazolyl‐based ketoximes by directly using readily available calcium carbide as an acetylene source, (Z)‐2‐azido‐1‐arylethan‐1‐one oximes as starting materials, and copper(I) chloride as a catalyst is described. The method provides a simple route to (Z)‐1‐aryl‐2‐(1H‐1,2,3‐triazol‐1‐yl)ethan‐1‐one oximes in good to excellent yields through [3+2] cyclization. The salient features of this protocol are the direct use of easy‐to‐handle acetylene source, inexpensive catalyst, high yield and simple work‐up procedures.