Trans-resveratrol establishes the planarity in its structure which makes it an interesting compound in both experimental and theoretical examinations. The current study, using the density functional method (DFT), attempts to compare the antioxidative capacities between hydroxyl (OH) and aromatic methine (CH) groups of this molecule. Becke’s exchange-correlation B3LYP functional together with 6-311++G(d, p) basis set was used to reveal the effects of structural geometry and electronic feature on the antioxidative results of OH and CH groups. The antioxidative action of trans-resveratrol has followed the HAT mechanism in gas, but the SPLET pathway in liquids. OH bond breaking is easier than CH bond disruption. 4-OH bond breaking induces the lowest BDE values of 74.4–77.9 kcal/mol in gas, acetone, methanol, and water, as well as the lowest PA values of 37.2–46.2 kcal/mol in acetone, methanol, and water. From the kinetic view, 4-OH is also an active center to capture laboratory radical DPPH, ROS radicals HOO• and CH3O•, and RNS radical •NO2.