A readily available chiral cyclohexanediamine‐derived bifunctional tertiary amine‐squaramide catalyst is more effective for the asymmetric dearomative 1,3‐dipolar cycloaddition of 2‐nitrobenzofurans and N‐2,2,2‐trifluoroethylisatin ketimines. A range of structurally diverse spiro‐fused polyheterocyclic compounds containing oxindole, pyrrolidine, and hydrobenzofuran motifs were smoothly obtained in excellent results (up to 99% yield, >20:1 dr in all cases and up to 99% ee). This method features high efficiency, mild reaction conditions, exquisite asymmetric induction, wide functional group tolerance, great potential for scale‐up synthesis, and attractive product diversification.