Instead of sluggish oxygen evolution reaction (OER), methanol oxidation reaction (MOR) is combined with hydrogen evolution reaction (HER) for efficient hydrogen production. Here, by data-driven and density functional theory (DFT) calculation, we establish a combined theoretical–experimental strategy for designing L12 ordered structures. Based on L12-PtNiTi, Hf element is added. Hf atoms occupy the α-site (face-centered site of FCC) with Pt. Ni atoms occupy the β-site (corner site of FCC) with Ti. The (PtHf)x(NiTi)100-x nano-alloy maintains L12 structure, enhancing intrinsic anti-poisonous performance and reducing Pt content. L12 (PtHf)50(NiTi)50/CNT exhibites an overpotential of 19 mV for HER and a mass activity of 4.725 A/mgPt for MOR in acidic electrolyte. For coupling HER with MOR, the working voltage is merely 0.55 V at 10 mA cm−2. It is demonstrated by DFT calculations that ordered (PtHf)50(NiTi)50/CNT has superior electrocatalytic performance attributed to smaller H adsorption energy, stronger OH binding energy and weaker CO adsorption energy.