An optical fiber made of quartz or glass and having a core and a cladding includes a microporous silica solution applied to an outer peripheral surface thereof, which is synthesized from a mixture of silicon alcoxide, active alcohol for facilitating hydrolytic action, alcohol, and water, by means of the sol-gel process, followed by baking to form a thin film of microporous silica made chiefly of silicon. Microporous of the thin film of microporous silica have function of cushioning to cushion and restrain that micro cracks much existing in the cladding undergo growth when the optical fiber is bent so that the optical fiber is likely to be broken. And the thin film of microporous silica which made chiefly of silicon has high heat-resistant properties similarly to the optical fiber itself. Accordingly, a heat-resistant optical fiber very excellent in heat-resistant properties is provided.