The crossover between two different conduction mechanisms (variable range and small polaron hoppings) is probed utilizing a conjunction of thermally varying conductivity and impedance in polycrystalline Pr2NiTiO6 (PNT). A combination of X-ray diffraction (XRD) and Raman spectroscopic investigations authenticates the lower symmetric monoclinic structure for PNT. The conductivity, impedance and relaxation spectra highlight the combined contributions of the electrodes, grain-boundaries and grain microstructures to the carrier dynamics in PNT. The relaxation mechanism has a non-ideal nature with distribution of relaxation times as observed from the dielectric and impedance spectroscopic data. The de resistivity investigation points towards a transition in the conduction mechanism showing a gradual crossover at temperature 490 K, from small polaron hopping to Mott's variable range hopping due to reduced activation energy.