Abstract Methyl formate (MF) is a valuable platform molecule, the industrial production of which is far from being green. In this contribution, TiO 2 ‐supported Pd( z )Pt(1− z ) catalysts were found to be effective in the green synthesis of methyl formate (MF)—at T =323 K and ambient pressure—through methanol (MeOH) oxidation. Two series of catalysts with similar bulk Pd/(Pd+Pt) molar ratios, z , were prepared; one by a water‐in‐oil microemulsion (MicE) method and the other by an incipient wetness impregnation (IWI). The MicE method led to more efficient catalysts owing to a weak influence of z on particle size distributions and nanoparticles composition. Pd( z )Pt(1− z )‐MicE catalysts exhibited strong synergistic effects for MF production but weak synergistic effects for MeOH conversion. The catalytic performance of Pd( z )Pt(1− z )‐MicE was superior to that of Pd( z )Pt(1− z )‐IWI catalysts despite the latter displaying synergetic effects during the reaction. The catalytic behavior of TiO 2 ‐supported Pd( z )Pt(1− z ) catalysts was explained from correlations between XRD, TEM, and X‐ray photoelectron spectroscopy characterizations.