The abundance of natural gas due to the advancements in exploration and extraction technologies has increased the interest in the direct conversion of methane to C2 molecules via oxidative coupling of methane (OCM) reactions [1]. The design of catalysts by tailoring shape and oxygen vacancies has a significant impact on their performance [2]. Within this context, in this work, the fine-tuning of structural defects of ceria rod-like and cube-like shaped nanoparticles were performed via La3+ doping (LaxCe1-xO2-x/2) in molar ratios of x=5-90 mol %. The morphology control was achieved by varying the hydrothermal synthesis temperature from 110 ??C to 180 ??C. The characterization of LaxCe1-xO2-1/2 catalysts was performed by SEM, HRTEM, XRD, and Raman spectroscopy. The catalytic performance of the new nanomaterials for the OCM reaction was studied at 750 ??C with an in-line gas chromatograph. In the LaxCe1-xO2-x/2 nanorods, the fluorite crystalline structure is essentially maintained even for x = 0.6. The Raman spectra analysis indicates that the addition of La3+ leads and increases the formation of different amounts of extrinsic and intrinsic oxygen vacancies. In addition, the catalytic tests for OCM reaction show that the LaxCe1- xO2-1/2 (x=50%) nanorods catalyst have 25% of CH4 conversion and 48% of selectivity for C2 products. The concentration of reactive oxygen species in the LaxCe1-xO2-1/2 (x=50%) nanorods was crucial to improving the conversion rates and selectivity.Funda????o de Amparo ?? Pesquisa do Estado de S??o Paulo (FAPESP)FAPESP: 17/11937-4