Titanium alloys, which are important in aerospace application, offer different properties via changing alloys. As design complexity and service demands increase, dissimilar welding of the titanium alloys becomes a particular interest. Linear friction welding (LFW) is a relatively novel bond technique and has been successfully applied for joining titanium alloys. In this paper, dissimilar joints with Ti-6Al-4V and Ti-5Al-2Sn-2Zr-4Mo-4Cr alloys were produced by LFW process. Microstructure was studied via optical microscopy and scanning electron microscopy (SEM), while the chemical composition across the welded samples was identified by energy dispersive X-ray spectroscopy. Mechanical tests were performed on welded samples to study the joint mechanical properties and fracture characteristics. SEM was carried out on the fracture surface to reveal their fracture modes. A significant microstructural change with fine re-crystallization grains in the weld zone (WZ) and small recrystallized grains in the thermo-mechanically affected zone on the Ti-6Al-4V side was discovered in the dissimilar joint. A characteristic asymmetrical microhardness profile with a maximum in the WZ was observed. Tensile properties of the dissimilar joint were comparable to the base metals, but the impact toughness exhibited a lower value.