Nanosized powders of trimetallic orthoferrites containing La and Sm in different ratios were synthesised by the thermal decomposition at low temperatures of the corresponding hexacyanocomplexes. The precursors and their decomposition products were analyzed by simultaneous thermogravimetric and differential thermal analysis (TG/DTA), x-ray diffraction (XRD) and Raman spectroscopy. Single phase trimetallic precursors and oxides were obtained. The crystal structure of the perovskitic oxides was orthorhombic, and the lattice parameters were affected by the ionic size of the rare earth elements present in the oxides. Raman spectroscopy showed a disorder effect in the vibrational bands with increasing the La content.