The orthorhombic nanostructured NdNiO3 is prepared by the sol-gel auto-combustion method, and its temperature-dependent magnetic and electrical transport properties are studied. The electric field emission with density functional theory and current voltage characteristics are also investigated at room temperature. The low-temperature magnetic measurement (magnetization with field and temperature) shows that NdNiO3 undergoes a magnetic phase transition (TN) near 176 K from paramagnetic to spin-canted antiferromagnetic state. The temperature-dependent magnetic susceptibility (χ) reinforced the signature of magnetic phase transition, and it is fitted by the modified Curie-Weiss law. A metal to insulator (MIT) phase transition (∼178 K) is observed above TN from temperature- and frequency-dependent conductivity measurement. It originates due to higher distortion of NiO6 octahedra and bandwidth constriction of NdNiO3 nanostructured compound. The variation of the frequency exponent (n) with temperature illustrates the continuous-time random walk conduction model with bipolaron condensation near MIT and the non-overlapping small polaron tunneling model above room temperature. The spin-resolved density of states calculation exhibits the room temperature paramagnetic phase and metallic nature and helps us to calculate local work function (φ) ∼5.44 eV. Low turn-on field at 1 μA/cm2 ∼10.5 V/μm and high field emission current density 203 μA/cm2 at 21 V/μm are observed for layered NdNiO3 with a field enhancement factor (β) ∼1230, which promotes NdNiO3 as an efficient field emitter. The current-voltage characteristics of NdNiO3/p-Si heterostructures are also explored for future technological applications.