A series of LaNiO3 materials were synthesized by the EDTA–citrate complexing method, modifying different physicochemical conditions. The LaNiO3 samples were calcined between 600 and 800 °C and characterized by XRD, SEM, XPS, CO-TPD, TG, DT, and N2 adsorption. The results evidence that although all the samples presented the same crystal phase, LaNiO3 as expected, some microstructural and superficial features varied as a function of the calcination temperature. Then, LaNiO3 samples were tested as catalysts of the CO oxidation process, a reaction never thoroughly analyzed employing this material. The catalytic results showed that LaNiO3 samples calcined at temperatures of 600 and 700 °C reached complete CO conversions at ~240 °C, while the sample thermally treated at 800 °C only achieved a 100% of CO conversion at temperatures higher than 300 °C. DRIFTS and XRD were used for studying the reaction mechanism and the catalysts’ structural stability, respectively. Finally, the obtained results were compared with different Ni-containing materials used in the same catalytic process, establishing that LaNiO3 has adequate properties for the CO oxidation process.