The complexation of boric acid (B(OH)3), the primary form of aqueous boron at moderate pH, with polyols is proposed and mechanistically studied as an efficient way to improve membrane processes such as reverse osmosis (RO) for removing boron in seawater by increasing the size of aqueous boron compounds. Computational chemistry based on the density functional theory (DFT) was used to manifest the reaction pathways of the complexation of B(OH)3 with various polyols such as glycerol, xylitol, and mannitol. The reaction energies were calculated as .80.6, .98.1, and .87.2 kcal/mol for glycerol, xylitol, and mannitol, respectively, indicating that xylitol is the most thermodynamically favorable for the complexation with B(OH)3. Moreover, the 1 : 2 molar ratio of B(OH)3 to polyol was found to be more favorable than the ratio of 1 : 1 for the complexation. Meanwhile, latest lab-scale actual RO experiments successfully supported our computational prediction that 2 moles of xylitol are the most effective as the complexing agent for 1 mole of B(OH)3 in aqueous solution.