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We have developed the Rh+/H8‐binap‐catalyzed chemo‐, regio‐, diastereo‐, and enantioselective intermolecular [2+2+2] cycloaddition of three unsymmetric 2π components. Thus, two arylacetylenes react with a cis‐enamide to yield a protected chiral cyclohexadienylamine. Moreover, replacing one arylacetylene with a silylacetylene enables the [2+2+2] cycloaddition of three distinct unsymmetric 2π components. These transformations proceed with excellent selectivity (complete regio‐ and diastereoselectivity and up to >99 % yield and >99 % ee). Mechanistic studies suggest the chemo‐ and regioselective formation of a rhodacyclopentadiene intermediate from the two terminal alkynes. [ABSTRACT FROM AUTHOR]