In the present study, dissimilar metal joints of SS321 and Ti–5Al-2.5Sn (α-Ti alloy) are produced by diffusion bonding at temperatures of 850, 900, and 950 °C under 10 MPa pressure for 30 min duration using a vacuum hot press (VHP). The interface of the joints was characterized through scanning electron microscopy coupled with energy dispersive spectroscopy and electron backscattered diffraction analysis for examining microstructure, morphology, and microchemistry across the interface. The effect of change in the heating process during diffusion bonding on the growth kinetics of interface layers was investigated. The interface of the joints comprised of intermetallic phases of σ phase, χ phase, (Fe,Cr)2Ti, FeTi and β-Ti. The joint produced at 900 °C has exhibited a maximum tensile strength of 315 MPa, 253 MPa, and 208 MPa at the test temperatures of −196 °C (77 K), room temperature (300 K), and 500 °C (773 K), respectively. Reduction in joint strength was noticed at test temperatures of RT and −196 °C for the samples bonded at a higher temperature of 950 °C due to the increased widths of the intermetallic phases at the interface. The effect of the bonding temperature on the tensile strength of the joints at an elevated test temperature of 500 °C was found to be negligible; however, the joints displayed good retention of strength along with substantial strain hardening followed by ductility at 500 °C. Fracture surfaces of RT and −196 °C tested samples showed the mixed mode of featureless smooth and cleavage fracture, whereas the 500 °C tested sample displayed planar interface failure. The zone of failure of the joints was noted to be around the interphase layer made of (Fe,Cr)2Ti + FeTi intermetallics.