A catalytic asymmetric formal 3+3 cycloaddition of 3‐indolylmethanol and an in situ‐generated azomethine ylide has been established to construct a chiral six‐membered piperidine framework with two stereogenic centers. This approach not only represents the first enantioselective cycloaddition of isatin‐derived 3‐indolylmethanol, but also has realized an unusual enantioselective formal 3+3 cycloaddition of azomethine ylide rather than its common 3+2 cycloadditions. Besides, this protocol combines the merits of a multicomponent reaction and organocatalysis, which efficiently assembles a variety of isatin‐derived 3‐indolylmethanols, aldehydes, and amino esters into structurally diverse spiroindoline‐3,4′‐pyridoindoles with one all‐carbon quaternary stereogenic center in high yields and excellent enantioselectivities (up to 93 % yield, >99 % enantiomeric excess (ee)). Although the diastereoselectivity of the reaction is generally moderate, most of the diastereomers can be separated by using column chromatography followed by preparative TLC. An unusual addition: The first catalytic asymmetric formal 3+3 cycloaddition of isatin‐derived 3‐indolylmethanol with an in situ‐generated azomethine ylide has been established to construct a chiral six‐membered piperidine framework with two stereogenic centers. This approach represents the first enantioselective cycloaddition of isatin‐derived 3‐indolylmethanol, and it has realized an unusual enantioselective formal 3+3 cycloaddition of the azomethine ylide (DCE = 1,2‐dichloroethane).