Subwavelength optical micro/nanofibers have been widely used as basic building blocks in the field of quantum sensing and quantum light source by virtue of their properties which include pronounced evanescent field, large surface area, and small optical mode area. This paper presents theoretical studies on the propagation properties of the guided optical wave and the spectral properties of entangled photons from spontaneous four-wave mixing in micro/nanofibers. We first analyze numerically single-mode propagation, field distribution, fraction of power, and group-velocity-dispersions by solving Maxwell’s equations with boundary conditions in cylindrical coordinates. Then, optical wave guiding properties of micro/nanofibers are applied to estimate the spectral properties such as central wavelengths and bandwidths of the created photons via spontaneous four-wave mixing that can be tailored by controlling diameter and length of micro/nanofibers. This theoretical work provides useful guidelines to design micro/nanofiber-based quantum sensing and quantum light sources for quantum technologies.