Perovskite nanocrystals are gaining increased attention because of their magnetic, transport and catalytic properties, and particularly there is a renewable interest of cobalt perovskites for catalysis. Accordingly, the correct interpretation of their properties stemming from a particular configuration of the cations within this crystalline structure is compulsory. Herein, we report the synthesis of Nd0.75Sr0.25CoO3 nanocrystals using the citrate sol-gel method and annealed at different final temperatures (600 °C, 700 °C, 800 °C and 1150 °C). Their characterization was carried out combining transmission electron microscopy, X-ray diffraction, Raman spectroscopy and vibrating sample magnetometry, demonstrating their complementarity to get the whole picture of the multi-featured perovskite-based nanocrystal behavior.