Establishing three-dimensional chemicals by using the C 2 -C 3 π bond of indoles has always been a research hotspot in organic synthesis; however, employing the oxidative C 2 -C 3 π bond of indoles to generate imine which would lead to the N 1 -C 2 π bond cyclization under metal-free conditions is still rare. Here, we report a bio-inspired synthesis of triazolo[1,2- a ]indolines by the oxidative cyclization between NH -indoles and azomethine imines with 3,3-dimethyldioxirane as the sole oxidant under metal-free and mild conditions. This finding represents an elegant instance of tri-functionalization of NH -indoles, which provides rapid access to a broad range of triazolo[1,2- a ]indolines with tetrahydroisoquinolines in one single step. Up to 86% yield and above 20:1 dr value are observed. The radical mechanism and proton migration process have been speculated.