The current examination dealt with the development of a methodology to produce quercetin, a multifunctional bio‐flavonoid, by designing task‐specific, highly acidic deep eutectic solvents, based on glycerol and natural organic acids. The purpose was to achieve a simultaneous hydrolysis of spiraeoside, the major quercetin glycoconjugate occurring in onion solid wastes, and quercetin extraction. After an initial performance screening, the combination of glycerol/oxalic acid was identified as the highest‐performing system, and further investigation showed that the most efficacious molar ratio was glycerol/oxalic acid 3:1. Further study of hydrolysis/extractions conditions suggested 30 min, at 130°C, to be the best operating conditions, giving the highest yield of 19.65 mg quercetin per grams of dry mass. The extract obtained under these conditions displayed significantly enhanced antiradical activity, compared to control extracts prepared with water or aqueous ethanol. On the other hand, results on the ferric‐reducing power were rather contradictory. It is proposed that such a methodology may be implemented to valorize onion solid wastes, for the production of extracts significantly enriched in quercetin, with increased antiradical properties.