Under appropriate cooling condition, intcrfacial phase appeared between α and β phases in Ti-5Al-2M0-3Zr alloy. Its thickness could reach 100 nm. The interfacial phase was either single layer structure or double layer structure. The monolithic layer adjacent to 3 phase was indentified as fee structure with relationship (110)β// (001)m, [11$\\mathop 1\\limits^{{\\rm{ - - }}} $]β /[110]m. The striated layer adjacent to a phase was indentified as hep with twin relationship {10$\\bar 1$1}<1$\\bar 0$12> to α. Thus, the study provided a new experimental fact for the controversial topic on structure of striated layer. Chemical composition of interfacial phase varied slightly with heat treatments, but always between that of α and β phases