The potential energy surfaces for the chemical reactions of group 14 carbenes have been studied using density functional theory (B3LYP/LANL2DZ). Five boryl(phosphino)-based carbene (B-Ë-P) species, where Ë = C, Si, Ge, Sn, and Pb, have been chosen as model reactants in this work. Also, four kinds of chemical reactions; intramolecular 1,2-migration, water insertion, alkene cycloaddition, and intermolecular dimerization, have been used to study the chemical reactivities of these group 14 carbenes. The present theoretical investigations suggest that the relative carbenic reactivity decreases in the order C > Si > Ge > Sn > Pb. That is, the heavier the group 14 atom (E), the more stable is the boryl(phosphino)-based B-Ë-P species towards chemical reactions. Our theoretical findings thus demonstrate that all boryl(phosphino)-based carbenes are isolable at room temperature because they are quite inert to chemical reactions, except that they are also moisture-sensitive molecules. Furthermore, the singlet-triplet energy splitting of the B-Ë-P, as described in the configuration mixing model attributed to the work of Pross and Shaik, can serve as a diagnostic tool for a better understanding and predicting of their chemical reactivities, kinetically and thermodynamically. The results obtained allow a number of predictions to be made.