The knowledge of C-COOH homolytic bond dissociation enthalpies (BDEs) is of great importance in understanding various chemical and biochemical processes involving the decarboxylation reaction. In the present study, the density functional theory (DFT method), B3P86/6-311++G(2df,2p)//B3LYP/6-31+G(d), is found to be reliable to predict the C-COOH BDE of various structurally unrelated carboxylic acids. The mean absolute deviation (MAD) and root-mean-square deviation (rmsd) of this optimal method are equal to 2.0 and 2.5 kcal/mol, respectively. With the authorized theoretical protocol in hand, an extensive C-COOH BDE scale containing over 100 carboxylic acids has been established, The availability of this body of data enabled a detailed investigation of remote substituent effect on four types of carboxylic acids, including para-substituted benzoic acid, beta-substituted cis-propenoic acid, beta-substituted trans-propenoic acid, and substituted propiolic acid. Also with the C-COOH BDE data obtained in this work, an excellent linear relationship has been found between the C-COOH BDE of carboxylic acids and the C-H BDE of their hydrocarbon analogues. After comparing the energy barrier of the Pd-catalyzed decarboxylation reaction (Delta G(decarboxylation)(double dagger)) with the related C-COOH BDE, a negative correlation between the Delta G(decarboxylation)(double dagger) and the C-COOL BDE was found.