Using first-principles methods, we studied formic acid dehydrogenation on the L11-type ordered Pt-based intermetallic compounds (i.e., X-Pt, X = Ag, Cu, Au, Pd, Ir, Rh, Tc, W, V). We found an adsorption-energy linear scaling relationship with positive slope between carbon monoxide (CO) and carboxyl (COOH) or hydrogen atom, but a weakly correlation with a negative slope for CO versus formate (HCOO) or CO versus hydroxyl (OH), which is attributed the beyond d-band-center model for the description of adsorption energies of HCOO and OH. And then, the selectivity of HCOOH dehydrogenation to HCOO (versus COOH) or COOH decomposition to CO2 (versus CO) on the Pt-based ordered alloys is regulated though breaking the adsorption-energy linear scaling relations of reaction intermediates. Our calculated results indicate that the L11-type CuPt is highly catalytic activity and selectivity toward formic acid decomposition and electrooxidation through the CO2 pathways of HCOOH→COOH+H→CO2+2H. This study underscores the importance of the unique adsorption-energy relations among reaction intermediates (e.g., CO versus OH) for screening high effective catalysts for hydrogen production of formic acid.