A hydrogen-resistant optical fiber particularly well-suitable for downhole applications comprises a relatively thick pure silica core and a depressed-index cladding layer. Interposed between the depressed-index cladding layer and the core is a relatively thin germanium-doped interface. By maintaining a proper relationship between the pure silica core diameter and the thickness of the germanium-doped interface, a majority (preferably, more than 65%) of the propagating signal can be confined within the pure silica core and, therefore, be protected from hydrogen-induced attenuation problems associated with the presence of germanium (as is common in downhole fiber applications). The hydrogen-resistant fiber of the present invention can be formed to include one or more Bragg gratings within the germanium-doped interface, useful for sensing applications.