We report on the synthesis and general physical properties of polycrystalline samples of LnNiO 3 (Ln=Pr, Nd, Sm). These compounds crystallize in a GdFeO 3 -type orthorhombically distorted perovskite structure, Pbnm space group symmetry, and reveal a first-order metal–insulator transition in a large range of temperatures varying from ∼130 to 400 K. The samples were prepared through three different methods: (1) the conventional ceramic process by mixing and reacting simple oxides; (2) through precipitation of hydroxides of Ln 3+ and Ni 3+ and (3) through sol–gel precursors. The samples were subjected to heat treatments at temperatures up to 1000°C and under oxygen pressures as high as 70 bar. Observations of the microstructure and measurements of X-ray powder diffraction XRD, electrical resistivity ρ(T), and differential scanning calorimetric DSC, indicated important effects that precursors from different methods have upon the final properties of these compounds. A comparison between these characterizations revealed that sol–gel precursors resulted in better quality samples of LnNiO 3 compounds.