Binary Ti-Al alloys containing 50 to 60 atomic percent aluminum are rapidly solidified by hammer anvil method under an argon atmosphere. Constituent phases in each alloy are identified by X-ray diffractometry and microstructures of the alloys are investigated using a transmission electron microscope. In alloys with aluminum content between 50 and 54 percent, a second phase exists besides TiAl(γ); this second phase is identified as Ti3Al(α2). The α2 phase is observed in two types of morphology. One is as fine lamellar alternating with γ and the other is as a particle. It is concluded that the existence of a metastable phase with the morphologies stated above should arise from a higher quenching rate attained by the hammer anvil method as compared to the conventional roll or splat-quench method. Implications of the above observation are discussed with respect to the phase relations in the Ti-Al binary system; these implications are still controversial in many respects.