The vinyl radical is one of the most unstable organic radicals. It is demonstrated that a nitro radical attacks phenylacetylene and makes the phenyl ring deconjugated with a double bond so that the resulting vinyl radical may be stabilized by delocalization to the phenyl ring鈥檚 蟺 orbital and easily trapped by TEMPO. It is noteworthy that all desired products were obtained in moderate to good yields in an (E)-configuration.