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The CO poisoning of the platinum anodic catalyst which typically functions the catalytic deterioration of the direct formic acid fuel cells could be minimized with a simple modification for Pt with titanium oxide. The fabrication scheme involved the spin-coating of a Ti precursor onto a Pt thin layer that was physically sputtered onto a Si substrate. The whole assembly was subjected to a post-annealing processing to produce the TiOx layer (60 nm) in a porous structure (mostly Anatase) atop of the Pt surface. The porous nature of the TiOx layer permitted the participation of Pt in the electrocatalysis of the formic acid electro–oxidation (FAO). The annealing temperature was critical in identifying the catalytic efficiency and durability of the catalyst toward the FAO. Interestingly, if compared to bare-Pt substrates, the TiOx-modified catalysts could successfully steer the FAO toward the direct dehydrogenation (favorable and less energetic) pathway with more than an order of magnitude increase in the catalytic activity. It also provided a great opportunity for the mitigation of poisoning CO; concurrently with a lowering (~0.3 V) in the onset potential of the FAO. The scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction spectroscopy (XRD), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques were all combined to evaluate, respectively, the catalyst’s morphology, composition, crystal structure and activity and further to understand the role of the TiOx in the catalytic enhancement.