An enantioselective one-pot Michael addition/hydroalkoxylation reaction between 2-hydroxy-1,4-naphthoquinones and alkyne-tethered nitroalkenes catalyzed by a cinchona-derived squaramide and a silver(I) salt has been developed. The sequential protocol provides a direct access to 4H-pyranonaphthoquinones in moderate to very good yields and good to excellent enantioselectivities at a very low catalyst loading (0.5 mol%) of the squaramide.