We have summarized our recent work in the area of novel silica-based optical fibers, which can be classified into two types: silica optical fiber doped with special elements including Bi, Al, and Ce, and micro-structured multi-core fibers. For element-doped optical fiber, the Bi/Al co-doped silica fibers could exhibit a fluorescence spectrum covering the wavelength range between 1000 and 1400 nm with a full width at half maximum (FWHM) of about 150 nm, which enables its use in fiber amplifiers and laser systems. The Ce-doped fiber’s center wavelengths of excitation and emission are about 340 and 430 nm, respectively. The sapphire-derived fiber (SDF) with high alumina dopant concentration in the core can form mullite through heating and cooling with arc-discharge treatment. This SDF can be further developed for an intrinsic Fabry-Perot interferometric that can withstand 1200 °C, which allows it to be used in high-temperature sensing applications. Owing to the strong evanescent field, microstructured multi-core fiber can be used in a wide range of applications in biological fiber optic sensing, chemical measurement, and interference-related devices. Coaxial-core optical fiber is another novel kind of silica-based optical fiber that has two coaxial waveguide cores and can be used for optical trapping and micro-particle manipulation by generating a highly focused conical optical field. The recent developments of these novel fibers are discussed.