(Chemical Equation Presented) Heteroatom-substituted alkynes such as ynol ethers and ynamines turned out to be decent substrates for the Nicatalyzed [3 + 2 + 2] cocyclization of ethyl cyclopropylideneacetate (1). The three-component cocyclization of 1, 1,3-diynes, and heteroatom-substituted alkynes also proceeded selectively. The study provided an efficient method for the synthesis of heteroatom-substituted cycloheptadiene and related compounds. © 2009 American Chemical Society.