Hydroxybenzoic acids (HBAs) and their anions play an important role in the food and pharmaceutical industries because of their antioxidant activity. In this study, we examined the mechanisms of the free radical scavenging action of HBAs and their anions using density functional theory (DFT) methods. Reaction enthalpies related to the mechanisms of free radical scavenging by the investigated species were calculated by DFT methods in water, DMSO, pentylethanoate, and benzene. Hydrogen atom transfer (HAT) is a preferred reaction pathway in benzene, while sequential proton loss electron transfer (SPLET) is a predominant reaction pathway in polar solvents, water, and DMSO for all species. For anions of HBAs, HAT and SPLET mechanisms in pentylethanoate are competitive, while SPLET is the most probable pathway in the case of HBAs.