A cost-effective, highly regioselective and metal-free version for the synthesis of indolizine derivatives by means of Tf2O-mediated cascade reaction of pyridyl-enaminones and thiophenols/thioalcohols under mild reaction conditions has been reported. Diverse electron-rich indolizine derivatives could be obtained in up to 94% yield via the selective 1,4-addition of vinyl iminium triflate tandem cyclization/aromatization, which allowed the simultaneous construction of C-N and C-S/and one example of C-Se bonds.