Alpha-benzoyloxypaeoniflorin (1), a new antioxidant monoterpene alpha-glycoside anomer was isolated from Paeonia suffruticosa along with known compounds, beta-benzoyloxypaeoniflorin (2), paeonolide, paeoniflorin and mudanpioside H. The structure of 1 has been determined by comparing spectral data with those of beta-benzoyloxypaeoniflorin (2). Compound 1 exhibited moderately potent radical scavenging activity on DPPH radical.