Design of electrocatalysts for the fundamentally important oxygen evolution reaction can be greatly aided by systematic structure activity tuning via composition variation. We have explored the iron cerium system as they are the most abundant transition and rare earth metals, and also due to the rnutualistic impact of their size and electronic attributes that can induce critical changes in the structure and electrochemical activity. Submicrometer thick films of a series of Fe(III)-Ce(III) phosphate(oxyhydroxide) (FeCePH) are fabricated using a soft chemical strategy involving surfactant-aided assembly, spin-coating, and mild thermal annealing. FT-IR, Raman, and Xray photoelectron spectroscopies, chemical analysis, X-ray diffraction, and electron microscopy reveal the systematic structural, electronic, and morphological variation, on tuning the iron cerium composition. Nitrogen adsorption-desorption studies show the surface area increasing and pore size distribution shrinking with the cerium content, indicating its structure-directing role. The electrocatalysis of water oxidation by FeCePH films on FTO-coated glass is studied in neutral pH conditions. The overpotential and Tafel slope decrease with increasing cerium content, reaching minima at the optimal Fe:Ce ratio of 1:0.5; the turnover frequency shows a corresponding increase and maximum. The trends are explained on the basis of the structural changes in the films, and the coupling of Ce3+ / Ce4+ with Fe3+/Fe4+ that leads to active state regeneration. This study presents a rational strategy to tune the efficiency of easily fabricated transition metal-based electrocatalyst thin films through rare earth metal incorporation; it should prove useful in the design of cost-effective catalysts for water oxidation.