Abstract A new protocol to access CF 3 ‐containing bispiro[isoquinolone‐pyrrolidine‐benzothiophenone]s was described. A series of 1,3‐dipoles were synthesized from isoquinolinetrione and CF 3 CH 2 NH 2 . In the presence of 10 mol% DABCO, the 1,3‐dipolar cycloaddition of isoquinolinedione trifluoroethyl ketimines and unsaturated benzothiophenones delivered corresponding adducts in excellent yields (up to 98 %) and diastereoselectivities (up to >20 : 1 dr).