The dry reforming of methane (DRM) has received critical attention because it converts two major greenhouse gases, methane and carbon dioxide, into molecular hydrogen and carbon monoxide, known as synthesis gas (syngas). Syngas is an important feedstock to produce various chemicals. A major drawback of the DRM process is the high deactivation rates of conventional nickel and cobalt catalysts. Experimental findings indicate that treating nickel and cobalt catalysts with boron reduces deactivation rates and enhances the catalytic activity. This study investigates the mechanism through which boron promotes catalytic stability using density functional theory calculations. First, the location of boron in nickel and cobalt catalysts is explored. Boron is found to be more stable occupying on-surface and substitutional sites in the catalysts. However, during DRM operation, carbon dioxide is able to oxidize on-surface and substitutional boron. The formed boron oxide units may react with each other and form diboron trioxide or react with hydrogen to form boric acid, and eventually leave the catalyst, which means they cannot have an effect on deactivation rates. This study argues that interstitial boron plays the major role since it is protected from getting oxidized by carbon dioxide. Geometric optimization indicates that interstitial boron leads to spontaneous surface reconstruction in both extended surfaces and nanoparticles. The effect of interstitial boron on the binding energies of methyl, hydrogen, carbon monoxide, and oxygen on extended surfaces and nanoparticles is studied and utilized using the Brønsted-Evans-Polanyi principle to give an insight about how boron reduces deactivation rates. Our analysis indicates that interstitial boron lowers the activation energies of methane and carbon dioxide. On (100) surfaces, boron lowers C–H activation energies in methane more than it lowers C=O activation energies in carbon dioxide, which means catalytic deactivation rates due to metal oxidation are lowered. On (111) surfaces, boron lowers carbon dioxide activation energies more than it lowers methane activation energies, which means catalytic deactivation rates due to coke formation are lowered. The computational study is consistent with experimental findings and gives an atomistic understanding of the beneficial role of boron on the DRM process catalyzed by nickel and cobalt.