To investigate the effect of Fe content on the correlation between the microstructure and mechanical properties in near-b titanium alloys, the Ti-5Al-5Mo-5V-1Cr-xFe alloy system has been characterized in this study. As the Fe content increased, the number of nucleation sites and the volume fraction of the α phase decreased. We observed a significant difference in the shape and size of the α phase in the matrix before and after Fe addition. In addition, these morphological deformations were accompanied by a change in the shape of the α phase, which became increasingly discontinuous, and changed into globular-type α phase in the matrix. These phenomena affected the microstructure and mechanical properties of Ti alloys. Specimen #2 exhibited a high ultimate tensile strength (1071 MPa), which decreased with further addition of Fe.