An organocatalytic asymmetric synthesis of directly linked benzothiazole‐dihydroimidazoles with two adjacent tertiary‐quaternary stereocenters through a Mannich‐type reaction of isocyanoacetates with N‐(2‐benzothiazolyl)imines is disclosed. When employing bifunctional dihydroquinine‐derived squaramide as catalyst, moderate to excellent yields (up to 97 % yield), moderate diastereoselectivities and excellent enantioselectivities (up to >99 % ee) were obtained for a variety of substrates. In addition, the transformation of the resulted directly linked benzothiazole‐dihydroimidazole into highly functionalized α,β‐diamino esters was also demonstrated. A practical and efficient transition‐metal‐free selective protocol has been developed for the direct synthesis of chiral directly linked benzothiazole‐dihydroimidazoles with two adjacent tertiary‐quaternary stereocenters through asymmetric Mannich‐type reaction of α‐isocyanoacetates with N‐(2‐benzothiazolyl)imines catalyzed by dihydroquinine‐derived squaramide under the mild conditions for the first time.