We demonstrate an efficient and sustainable strategy for the direct synthesis of 2,4-disubstituted quinazolines by arene Ru(II)benzhydrazone complex via the eco-friendly sequential acceptorless dehydrogenative coupling of 2-aminobenzhydrol derivatives and benzyl alcohols for the first time. The new ruthenium(II) complex of the general formula [(η6-p-cymene)Ru(L1)Cl] (L1-acenaphthenequinone hydrazone) has been synthesized and characterized by analytical, spectroscopic, and single-crystal X-ray diffraction techniques. A broad spectrum of 2,4-disubstituted quinazolines have been successfully derived (25 examples) from 2-aminobenzhydrol derivatives with various benzyl alcohols using 1 mol % of catalyst loading in the presence of NH4OAc. The present protocol is highly selective and produces a maximum yield of 95% under mild reaction conditions. The different reaction intermediates detected through control experiments such as aldehyde, 2-aminobenzophenone, benzylidene(amino)phenylmethanone, and 1,2-dihydroquinazoline are isolated and authenticated by the NMR study. Gratifyingly, the coupling reaction is a simple and atom economic with the release of water and hydrogen gas as the only byproducts. A gram-scale synthesis of 2-(4-methoxyphenyl)-4-phenylquinazoline illustrates the synthetic utility of the present protocol.