This research provides the first known procedure for cleanly and consistently reducing the diameter of single-crystal sapphire optical fiber (SCSF) below the limits of standard production methods, including the first production of subwavelength-diameter optical fiber (SDF) composed of single-crystal sapphire. The first known demonstration of an air-clad single crystal sapphire optical fiber demonstrating single-mode behavior is also presented, and the single-mode cutoff wavelength and diameter are determined. Theoretical models describing and predicting the optical behavior of low modal volume sapphire optical fibers are also presented. These models are built upon standard weakly-guiding optical fiber theory, which is found to be accurate once experimentally-determined properties of the SCSF are substituted for theoretical values. Reduced modal dispersion is also observed in the form of decreased laser pulse broadening in reduced-diameter SCSF. The improvements in spatial resolution for distributed sensing systems such as Raman distributed temperature sensing are also predicted based on the measured decrease in pulse duration. This research also provides an enhanced understanding of the etching behavior of sulfuric and phosphoric acids on sapphire surfaces, including the first reporting of etching rates and activation energies for a-plane sapphire surfaces. Morphological changes of sulfuric and phosphoric acids at and beyond the temperature ranges used in etching were also tested and discussed in detail, especially regarding their practical impact on observed etching behavior. The demonstration of LMV single-crystal sapphire optical fibers enables the adaptation of numerous sensing schemes requiring low modal volume or single-mode behavior to be utilized in extreme environments. / Ph. D.