The effect of annealing temperatures on the structural and the electrical transport properties of La2NiMnO6 nanoparticles is investigated in detail. The grain size, grain boundary and the antisite disorder (ASD) are affected by the annealing temperature during the preparative conditions of annealing. The HRTEM image indicates that the average grain size increases with annealing temperature providing a platform for explanation of the transport data. Both I−V and dIdV−V measurements show that the electrical conduction is non‐Ohmic and characterized by a voltage V0true(ATtrue), known as the onset voltage, which scales with the Ohmic conductance Σ0true(ATtrue) as V0true(ATtrue)∼Σ0true(Ttrue)xAT, xAT being the onset exponent having negative values in both cases. AT refers to the fact that Σ0true(ATtrue) is changed by the annealing temperature (AT). V0true(ATtrue) depends strongly on the grain size and grain boundaries and decreases with the increase in annealing temperature. The negative value of xAT is physically understood from the concept of inter‐granular tunneling effect. This non‐Ohmic conduction, onset voltage V0true(ATtrue) and onset exponent xAT are qualitatively explained by considering the conduction through both the ordered and disordered regions and by applying Glazman–Matveev model. The transport data are systematically analyzed within the framework of scaling formalism.