The C-O homolytic bond dissociation enthalpies(BDEs) were calculated by high-level ab initio including G4, G3B3, G3, CBS-QB3 and a series of density function theory (DFT) methods. It is found that the wB97 method gave the most reliable C-O BDEs and the root-mean-square deviation (RMSD) is 7.6 kJ/mol. Therefore, the C(sp(2))-O BDE predictions and the substituent effects of alkenyl phosphates/sulfonates and aryl phosphates/sulfonates were investigated in detail by using the wB97 method. Interestingly, there exist different substituent effects in alpha- and beta-substituted alkenyl phosphates/sulfonates. Excellent linear relationships between the C-O BDEs of beta-substituted alkenyl phosphates/sulfonates with substituent constant sigma(+)(P) were found. In addition, the NBO analysis further disclosed the essence of the substituent effects on C-O BDEs.