Tf₂NH-assisted BINAM-derived thiophosphoramide catalysis has been accomplished for the enantioselective oxysulfenylation of o-vinylanilides with N-(aryl/alkylthio)imides. The developed reaction offers access to diverse substituted aryl/alkylthio tethered 3,1-benzoxazines in excellent yields and enantiomeric ratios. Furthermore, synthetic applications of benzoxazines and aryl/alkylthio moieties and a transition state model for the observed enantioselectivity are also discussed.