La0·8Sr0·2MnO3 (LSM) perovskite as oxygen electrode material for the reversible solid oxide fuel cells (ReSOFC) was synthesized by the fast solution combustion method and assessed for subsequent calcination influence. The microstructural, morphological, compositional and optical properties of the obtained material were analyzed with X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM) coupled with an energy-dispersive X-ray spectroscopy detector (EDS) and UV–visible spectroscopy techniques. The XRD results showed the coexistence of rhombohedral R-3c and Pm-3m polymorphs for the perovskite phase, with a decreased fraction of the cubic phase as the temperature and/or time used for the calcination were increased. The HR-TEM images confirmed the existence of the R-3c and Pm-3m polymorphs for the sample subjected to calcination at 1300 °C, showing that the rapid combustion method did not allow the pure formation of the La0·8Sr0·2MnO3 phase for the calcination temperatures below 1400 °C, due to the swiftness of the combustion synthesis 500 °C for 5 min. The average grain size was found to be increased with the calcination time. The EDS analysis depicted a better agreement in stoichiometry with the theoretical composition. The apparent porosity was decreased with the increase in the temperature and calcination time due to the coalescence of the sintering pores. The sample obtained after the calcination at 1400 °C for 8 h exhibited 1.6% of porosity. The hardness was improved with the higher calcination time and temperature and reached a maximum value of 5.7 GPa that merely matched the bulk density. A similar trend was observed in the temperature dependence resistivity studies and all the samples presented a low resistivity of ∼1.2 Ω cm in the temperature range of 600–700 °C. The optical characterization exhibited a broad absorption in 560–660 nm.