Results from theoretical calculations of O-16/O-18 equilibrium isotope effects (EIEs) on deprotonation of phosphate and methyl phosphate monoanions as well as their deuterated counterparts are reported. The EIEs are calculated from the Bigeleisen equation using harmonic vibrational frequencies from several quantum mechanical methods (HF, DFT, MP2, and AM1). All methods correctly predict the qualitative trends in the EIEs related to the different isotope substitutions. However, the calculated gas-phase values are found to be systematically higher than those experimentally observed in aqueous solution. On the other hand, the addition of explicit solvent molecules (up to 24 waters) in the first solvation shells of the phosphate ion substantially improves the calculated EIE, which approaches the experimental value with increasing size of the water cluster. The large effects of surrounding water molecules on the phosphate deprotonation EIE can be explained by the strong solute-solvent interactions, which result in solvent coupled vibrational modes of the phosphate ions.