In this study, a new method for isolation of polyphenols (PP) from spent coffee grounds (SCG) and coffee silverskin (CS) is described. The method consisted of a mild hydrothermal pretreatment at 120°C, for 20 min, using a liquid-to-solid ratio of 20 mL/g. PP (determined as gallic acid equivalents, GAE) were the most abundant components in the extracts produced by this method, corresponding to 32.92 mgGAE/gSCG and 19.17 mgGAE/gCS, among which flavonoids corresponded to 8.29 and 2.73 mg quercetin equivalents/g of SCG and CS, respectively. Both extracts presented antioxidant activity but the results were higher for SCG extract, probably due to the highest content of PP present. Negligible effects (less than 1% solubilization) were caused by the hydrothermal pretreatment on cellulose, hemicellulose, and protein fractions of these materials. Some mineral elements were present in the extracts, with potassium being the most abundant. Hydrothermal pretreatment under mild conditions was demonstrated to be an efficient method to recover antioxidant PP from coffee residues.