Mesoporous alumina, as a porous, high specific surface area, high activity, and heat stable material, has been widely used as an industrial adsorbent, catalyst, and catalyst support. The modification of alumina with organic polymers has been widely investigated in recent years. In this study, we compared the dependence of the adsorption of a polyelectrolyte, poly(acrylic acid) (PAA) on γ-alumina particles on polymer size via Fourier transform infrared spectroscopy, thermogravimetry, nitrogen adsorptiondesorption isotherm analysis, and atomic absorption spectrophotometry. We found that PAA with a hydrodynamic diameter greater than the alumina pore size would only adsorb on the outer surface of the oxides. For polymers with hydrodynamic diameters smaller than the alumina pore size, PAA infiltration resulted in a monolayer coverage of both the outer and inner surfaces of the oxide. Among the three PAA that could infiltrate the alumina pores, the one with the smallest molecular weight showed the highest adsorbed amount on alumina. The temperature, pH, concentration, and ionic strength of the PAA solutions were varied to illustrate the physicochemical differences of the prepared polymer/oxide composite materials. The high PAA-loaded composites were treated with a nickel ion solution, converted to Ni/alumina catalysts, and used in the methanation of carbon dioxide. The Ni/alumina catalysts were analyzed with X-ray diffraction and temperature-programmed reduction to illustrate the structural characteristics. The catalytic CO 2 methanation of the catalyst samples revealed that a solution pH value higher than pK a of PAA favored the formation of catalysts with high catalytic activity.