A squaramide catalyzed asymmetric Michael/Mannich [3+2] cycloaddition reaction between N‐2,2,2‐trifluoroethyl isatin ketimines and barbiturate‐based olefins was developed. The corresponding trifluoromethylated dispirobarbituric acid derivatives containing three stereocenters were obtained in excellent yields and stereoselectivities (up to 99% yield, 99:1 dr and >99% ee). In addition, the gram‐scale reaction also achieved with excellent yield and stereoselectivity.