A new tert-butyl radical-induced 1,2-alkynyl migration reaction is reported. By using the characteristics of in-situ-generation of tert-butyl radical from pivalaldehyde mediated by di-tert-butyl peroxide (DTBP), tert-butyl radical-triggered addition and alkynyl migration of the preformed 1,4-enynes led to the synthesis of a series of α-alkynyl ketones with good to excellent yields, thereby realizing alkylalkynylation of unactivated olefins. Based on the experimental results and literature reports, a possible reaction mechanism is proposed, which involves tert-butyl radical-triggered addition, 3-exo-dig cyclization of anti-"Baldwin" rule and alkynyl migration process. This reaction has the advantages of high functional group compatibility, metal-free conditions, and simple operation, which provides a feasible and effective synthetic strategy for the bifunctionalization of unactivated olefins.