Despite crystalline bismuth and nickel being not superconducting, Bi/Ni bi-layers show a superconducting transition at about 4 K and this has been attracting attention. There are different interpretations for the superconductivity (SC) in Bi/Ni, for example: the presence of Ni induces the modification of Bismuth structure from rhombohedral to face centered cubic (FCC); magnetic fluctuations at the interface of Ni/Bi would induce SC; formation of intermetallic NiBi3 at the interface; Bi induced superconductivity in Ni layer and formation of a very thin amorphous Bi layer formed at the interface of Ni/Bi. The present work studies the SC and microstructure modifications of the Bi/Ni bilayer and nanoparticle systems by means of electric transport and magnetic measurements, and high resolution electron microscopy (HRTEM). Two-step transitions have been observed in Bi/Ni bilayers. The observed microstructure shows that two intermetallic phases (NiBi and NiBi3) have been formed during the sample preparation by pulsed laser deposition. The formation of the two intermetallic compounds constitutes the origin of the superconductivity in Bi/Ni systems. One interesting phenomenon is the observation of Bi-rich phase (NiBi3) formed near the Ni layer. However, the Ni-rich phase (NiBi) is formed after the NiBi3 layer. Energy dispersive X-ray spectroscopy (EDXS) results at nanometer scale clearly show an unusual increase of Ni concentration near the interface of Bi/Substrate, which was confirmed by HRTEM observation. Bilayers of Bi/Ni nanoparticles and Ni/Bi nanoparticles have been studied as well and the samples do not show a full superconducting transition. On the other hand, Bi/Ni bilayers and Bi/Ni/Bi trilayers have been prepared at 4.2 K by thermal evaporation do not reveal formation of intermetallic compounds even after annealing at 300 K, and they are not superconducting down to 1.8 K . With this result, The SC in Ni/Bi thin films can be explained by the formation of NiBi and NiBi3 due to interdiffusion at the interface.