In this work, the effects of Sb doping on the electrical conductivity of fine-grain 0.9(K0.5Na0.5)(Nb1−xSbx)O3-0.1Bi(Ni2/3Nb1/3)O3 (KNNSx-BNN) ceramics were systemically investigated. It was found that the grain size decreases from ~900 nm (x = 0) to ~340–400 nm (x = 0.06–0.08), and then increases again to ~700 nm (x = 0.10). This is because the solubility limit of Sb doping is about 0.08 in this ceramic, and more Sb doping will facilitate the grain growth as the sintering aids. Impedance and conductivity analyses reveal that the grain resistance and its activation energy show a similar changing tendency with grain size, while grain boundary conductivity steadily increases after Sb doping. In this process, the grain contribution on ceramic conductivity changes with grain size variation, and grain boundary contribution becomes more obvious with increasing doping content. The reduction in grain size, improvement in grain boundary density and doping ions entering into the grain boundary should contribute to the evolution of electrical conductivity properties after Sb doping in KNN-based ferroelectric ceramics.