This study investigated the changes in the physiochemical property, phytochemical content, nutritional content and antioxidant activity of Polygoni multiflori Radix by steam, aging, and fermentation. After processing Polygoni multiflori Radix (PMR), pH slightly decreased, while acidity increased (pH 5.70→4.78, acidity 0.23→0.29%). The reducing sugar content increased after aging and fermentation from 1.19 mg/g (PMR) to 1.40 (fermented PMR, FPMR), 1.30 (red PMR, RPMR), 1.53 (fermented red PMR, FRPMR), 1.99 (black PMR, BPMR), and 2.33 mg/g (fermented black PMR, FBPMR). Total phenolic content was highest in PMR (6.05 mg/g) and total flavonoids and maillard product were increased after aging and fermentation of PMR, and were the highest in BPMR (1.60 mg/g) and FBPMR (2.76 O.D.), respectively. The major phytochemical was 2,3,5,4'-tetrahydroxystilbene-2-0-α-glucoside, which were highest in PMR (64.9 mg/g) with 46.47 mg/g at FPMR, 33.94 mg/g at RPMR, 48.76 mg/g at FRPMR, 36.68 mg/g at BPMR and 34.35 mg/g at FBPMR. The main fatty acids and free amino acids were detected as palmitic acid (C16:0) and proline, respectively. Generally, 2,2-diphenyl-1-picrylhydrazyl and 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt radical scavenging activities and FRAP reducing powers were shown high in PMR (39.06%, 98.32%, and 2.61 O.D. in extracts concentration 1.0 mg/mL), then were decreased after aging and fermentation.