The acceptorless dehydrogenation reaction is a sustainable and atom‐economical methodology in organic synthesis, resulting in the byproducts of only hydrogen or water. Herein, a robust Co‐Si/CN catalyst (derived from ZIF@SiO2 composite) has been synthesized through a one‐step assembly process via pyrolysis and etching. This catalyst has been employed for the acceptorless dehydrogenative coupling of 2‐aminoalcohols with secondary alcohols, enabling efficient conversion of various substrates into desired quinoline or pyridine derivatives with a yield of up to 94%