We report here versatile methods to engineer the microstructure and understand the fundamental physicochemical properties of CeO2 to improve its catalytic viability for practical applications. In this context, different morphologies of CeO2 are synthesized using tailored homogeneous precipitation methods and characterized by XRD, BET, SEM and TPR methods. The shuttle-shaped CeO2 prepared under hydrothermal condition shows higher surface area and low-temperature reducibility. The 0.5 wt% Pt-impregnated shuttle-shaped CeO2 shows lower-temperature CO oxidation behaviour as compared to its bulk-like CeO2 (with 0.5 wt% Pt) counterpart, synthesized by conventional-reflux method. Further, nanorod morphology of CeO2 prepared with Cl- as counter ion shows lower-temperature oxidation of soot as compared to the mesoflower morphology of CeO2, prepared with NO 3-3 as counter ion in the reaction medium. Further, linear sweep voltammetry, chronopotentiometry and CO-stripping voltammetry studies are performed to evaluate the promoting activity of CeO 2 to Pt/C for ethanol electro-oxidation reaction in acidic media. Results show that CeO2 provides active triple-phase-interfacial sites for suitable adsorption of OH species which effectively oxidize the CO ads on Pt/C. The results presented here are significant in the context of understanding the physicochemical fine prints of CeO2 and CeO2 based hetero-nanocomposites for their suitability to important catalytic and energy-related applications. © 2014 Indian Academy of Sciences.