In this research, a novel titanium metallic composite, Ti6Al4V powder mixed with 5 at.% Nb powder, was fabricated by selective laser melting (SLM). The effect of Nb addition on their phase transformation, microstructure evolution, mechanical properties, and corrosion behavior were studied. Interestingly, the novel alloy shows a combination of superior plastic deformation (εp= 18.9 ± 1.8%) and high compressive strength (σc= 1593 ± 38 MPa), which is 60.2 and 3.2% higher than that of the SLM-processed Ti6Al4V alloy under optimum printing parameters, respectively. However, the yield strength of Ti6Al4V + 5Nb (973 ± 45 MPa) is lower than that of the Ti6Al4V alloy (1066 ± 12 MPa). The solidification mechanism changes from planar to cellular mode with Nb addition. The ultrafine microstructure β grains are observed, which show a columnar shape and cellular shape. More importantly, the volume fraction of the β phase is significantly increased from 3.7% to 20.4% because of the Nb addition. In addition, the Ti6Al4V + 5Nb alloy possesses better corrosion resistance than the Ti6Al4V alloy. The research highlights that the addition of Nb powder in Ti6Al4V processed by SLM can improve the mechanical properties and corrosion resistance of the material.