Skeletal reorganization is a type of intriguing processes for their interesting mechanism, high atom-economy and synthetic versatility. Herein, we describe an unusual skeletal reorganization divergence of N-sulfonyl ynamides. Upon treatment with lithium diisopropylamine (LDA), the N-sulfonyl ynamides could undergo a skeletal reorganization to deliver thiete sulfones, while the additional use of DMPU would shift the process to furnish propargyl sulfonamides. Mechanistically, these processes are proposed to initiate from a lithiation/cyclization cascade, and the following ligand-dependent 1,3-sulfonyl migration or β-elimination would constitute the divergence. Therefore, this protocol not only represents a new skeletal reorganization mode, but also provides a facile access to privileged molecules from the easily accessible ynamides.