This study presents a highly efficient and cost-effective Cu/CeO2 catalyst for the acceptorless dehydrogenative coupling (ADC) of o-aminobenzyl alcohols and secondary alcohols to synthesize quinolines. The catalyst demonstrated over 90% yield in quinoline production under mild conditions, exhibiting excellent tolerance to various functional groups. The Cu/CeO2 catalyst, synthesized via a co-precipitation method, was thoroughly characterized through various techniques like PXRD, XPS, and AC-STEM. Control experiments confirmed the ADC pathway, where both alcohol substrates underwent dehydrogenation, forming key intermediates that subsequently condensed to produce quinolines. This catalytic system, offering recyclability and high efficiency, is a promising alternative to noble metal-based catalysts for sustainable quinoline synthesis.