The interfacial properties between fiber and matrix play a critical role in the overall mechanical responses of composite materials. In this paper, the glass fiber-mortar interfacial microstructure in fiber reinforced concrete (FRC) is visualized and characterized using X-ray microscopy. Additionally, three types of fiber-mortar interface (glass fiber, high modulus polyvinyl alcohol (PVA) fiber, and basalt fiber) are analyzed by scanning electron microscopy and energy dispersive X-ray spectroscopy. The results revealed a lot of microcracks along with the glass fiber-mortar interface; moreover, the hydration product of the glass/PVA/basalt fiber-mortar interface was much lower than that of the mortar matrix. Because microcracks or lower hydration product have such a negative effect on the interfacial bonding between fiber and mortar, the objective of this paper was to provide an analysis of this problem through extensive testing of their bonding properties. Specimens made of three types of fiber were tested along with three different mortar types under tensile stress and a combined stress state to investigate the interfacial bond properties between fiber and mortar. Results show that both of the tensile and shear bond strength of the interface were not only improved by stronger mortar matrix, but also significantly affected by fiber type. Furthermore, when the interface failed by slipping along the interfacial area, the interface showed an increasing shear bond strength with the increase of compressive stress. This was not the case when failure was due to the crushing of mortar. Finally, the FRC splitting tensile strength was tested to demonstrate the bonding mechanism effects on the FRC mechanical properties.