The NHC-catalyzed conjugate hydroacylation of 1,4-naphthoquinones allows for the synthesis of monoacylated 1,4-dihydroxynaphthalene derivatives. These targets, difficult to prepare selectively by standard protocols, represent important intermediates in the elaboration of highly substituted 1,4-naphthoquinone derivatives, which constitute relevant pharmaceutical scaffolds. High regioselectivity has been observed in the hydroacylation reaction when starting from nonsymmetrical quinones.