In this manuscript, we present the synthesis of gadolinium orthoferrite nanoparticles using the sol–gel auto-combustion technique. The obtained gadolinium orthoferrite nanoparticles were annealed at various temperatures, such as 800 °C, 900 °C, 1000 °C, and 1100 °C. The synthesized materials were analyzed by various instrumental characterizations. The vibrational characteristics of the synthesized samples were verified by FTIR. The surface morphology of the gadolinium orthoferrite nanoparticles was analyzed by FE-SEM and HR-TEM, revealing their spherical structural morphology and uniform particle structure. The presence of the elemental features was analyzed in the gadolinium orthoferrite nanoparticles by EDAX. The surface analysis of the core ranges of the XPS-recorded spectra were obtained for the elemental states of the Gd, Fe, and O factors in the samples, and it additionally characterized the different levels of oxidative states by fitting the levels of the high-resolution parameters of Gd 4d, Fe 2p, and O 1s. The magnetic properties of the samples were investigated by VSM. The measurement of the magnetic parameters revealed that gadolinium orthoferrite nanoparticles exhibit a ferromagnetic nature.