Abstract: A programmable algorithm using bond dissociation energies has been proposed for the prediction of reaction pathways. It has been successfully applied to a gas-phase reaction of F₂+CH₃Cl, with the accurate revelation of the most favorable product CF₄ and its corresponding reaction pathway. This acts as an inspiring example of chemical empiricism 2.0, and may open the door for the large-scale prediction of reaction pathways at the age of big data.