The multi-pass deposited metals were prepared by metal-cored wire with low (2.5 wt%) and high (4.0 wt%) Ni to research the effect of Ni on the bainite/martensite transformation. Results showed that deposited metals exhibited a multiphase structure comprised of bainite, martensite and residual austenite, which is not only explained from SEM/TEM, but also identified and quantified each phase from crystallographic structure through XRD and EBSD. With Ni content increasing, the fraction of martensite increases from 37% to 41%, and that of bainite decreases from 61% to 55% accordingly because 4% Ni element narrows the temperature range of the bainite transformation ~20 °C. The 7.8% residual austenite exhibited block and sheet in the deposited metal with low Ni, while the fraction of residual austenite was 3.26% as a film with high Ni, caused by different transformation mechanisms of bainite and martensite. The tensile strengths of deposited metals were 1042 ± 10 MPa (2.5% Ni) and 1040 ± 5 MPa (4% Ni), respectively. The yield strength of deposited metals with high Ni was 685 ± 18 MPa, which was higher than low Ni due to the high fraction of martensite. The impact values of deposited metals with high Ni content decreased because the volume fraction of bainite and residual austenite and area fraction of large-angle grain boundary were lower.