Homogeneous and transparent enstatite fibers were prepared via the sol-gel process of metal alkoxide precursors. The gel-to-ceramic conversion was characterized. The solution compositions had a significant influence on the microstructural evolution of gel fibers. Infrared studies indicated that bidentate bridging ligands were formed between acetate and metal ions, which enhanced spinnability remarkably. The as-drawn fibers were essentially microporous. On heating to 800 oC, enstatite ceramic fibers exhibited mesoporous structures with nanocrystals in size. The optical transmittance of enstatite ceramic fiber in the visible range was around 90 % after heating at 800 oC.