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The microstructure of melt extracted Ti-44Al-8Nb-0.2W-0.2B-1.5Si fiber were investigated. When the rotation speed increased from 2000 to 2600 r/min, the appearance of the wire was uniform with no Rayleigh-wave default. The structure was mainly composed of fine α2 (α) phase dendritic crystal and a second phase between dendrite arms and grain boundaries. The precipitated second phases were confirmed to be Ti5Si3 from the eutectic reaction L→Ti5Si3 + α and TiB. As the lower content of Si and higher cooling rate, a divorced eutectic microstructure was obtained. Segregation of Ti, Nb, B, Si, and Al occurred during rapid solidification.