KOtBu mediates the reaction between 2‐amino arylcarbaldehydes and benzyl/alkyl cyanides toward the expeditious formation of 2‐aminoquinolines under transition‐metal‐free conditions. The described transformation proceeds through in‐situ generated enimine intermediate from benzyl/alkyl cyanides under KOtBu‐mediated reaction conditions. The substituted 2‐aminoquinolines were realized in excellent yields at room temperature and shorter reaction time. The designed process exhibits operational simplicity and broad functional group tolerance in delivering the products of high significance. KOtBu‐mediated protocol has been described for the comprehensive synthesis of 2‐Aminoquinolines using benzyl/alkyl cyanides and 2‐amino arylcarbaldehydes. The developed domino reaction conditions holds good for wide range of substrates by giving the desired products in excellent yields at room temperature and shorter reaction time.