The effect of nickel oxide additive on the smelting behaviors of chromium-bearing vanadium titanomagnetite pellets (CVTP) was investigated while analyzing the transfer behavior of nickel in iron and slag. The results show that when NiO added to CVTP increases from 0 to 6 wt.%, softening start temperature increases from 1148 to 1212 °C, and the softening end temperature increases from 1280 to 1334 °C; the melting start temperature increases from 1318 to 1377 °C, and the dripping temperature decreases from 1558 to 1521 °C. The pig iron comprises a compound of Fe-Ni-C. The slag structure depolymerizes with increasing nickel addition. The softening-melting behaviors of CVTP, the reduction of nickel into pig iron, and the depolymerization of slag structure indicate the feasibility of producing nickel-iron alloy through the blast furnace process.