Agricultural residues Castanea mollissima shells represent a promising resource for natural pigments for the food industry. This study provides a comprehensive and systematic evaluation of water-soluble pigments (CSP) from C. mollissima shells, which were obtained by 50% ethanol with microwave-assisted extraction. Spectroscopic techniques (UV, FT-IR, (13)C NMR), elemental analysis, and chromatographic techniques (HPAEC, GPC) revealed that the main components in the CSP were flavonoids procyanidin B3 (condensed tannin), quercetin-3-O-glycoside, and steroidal sapogenins. As a consequence, CSP was water-soluble and presented significant DPPH scavenge capacity (EC50 value was 0.057 mg/mL). Specially, CSP gave excellent antibacterial activity, and even better than 5% aqueous phenol in some case. Moreover, CSP was practically nontoxic and exhibited good stability with temperature, natural light, and metal ions. These outstanding properties will enlarge the application of CSP for natural food additives production.