The synthesis of a nano-dimensional cluster of PrFeO3 orthoferrite with interesting tunable characteristics is the principal objective of this work. We document a very simple and improved co-precipitation method to synthesize nanoparticles of the desired dimension of rare earth substituted orthoferrite PrFeO3. The structural distortion is analyzed with Powder X-ray diffraction, which explores a distorted perovskite crystallized ferrite with space group Pbnm (62). The electrical behaviour of the prepared sample is investigated in a frequency range of 50 Hz to 5 MHz at different temperatures. A shift in the dielectric behaviour is noticed at about 250 °C. The morphological structure of the sample explored with High Resolution Transmission Electron Microscope (HRTEM), portraits a nano clustered structure. The magnetic properties of PrFeO3 are observed with Vibrating Sample Magnetometer (VSM) at 20 K and 300 K. A Very interesting change in magnetization is noticed at about 172 K–200 K. The effect of temperature on magnetic properties of PrFeO3 is reportedly due to the spin reorientation transition from Γ2 →Γ4 at TSR ≈ 172 K–200 K temperature range. The electronic band structure of nanoscale PrFeO3 with spin up and spin down states of antiferromagnetic nature is reported. PrFeO3 also exhibit multiferroic properties. © 2019 Elsevier B.V.