Superconductivity in bulk rhombohedral Bi has recently been detected to appear below 0.53 mK and 5.2 μT. Here, we unambiguously demonstrate that superconductivity in rhombohedral Bi can be greatly enhanced by incorporating Ni ions onto the Bi sites and reducing the size to the nanometer scale. The superconducting transition temperature T C of 12 nm rhombohedral Bi nanoparticles (NPs) reaches 4 K at ambient pressure. T C is significantly enhanced to reach 7, 12, and 18 K in 6, 8, and 10% Ni-doped Bi NPs, respectively, where superconductivity is found to coexist with ferromagnetism. Ni-doping causes a significant amount of electronic charges to shift toward the interconnecting regions between neighboring Bi ions. First-principles calculations reveal that the Ni ions serve as charge and spin suppliers for the developments of superconductivity and ferromagnetism.