This study investigates the impact of polyvinyl alcohol (PVA) fibers on the mechanical properties and durability of high-performance shotcrete (HPS). Results demonstrate that PVA fibers have a dual impact on the performance of HPS. Positively, PVA fibers enhance the tensile strength and toughness of shotcrete due to their intrinsic high tensile strength and fiber-bridging effect, which significantly improves the material’s splitting tensile strength, deformation resistance, and toughness, and the splitting tensile strength and peak strain have been found to be increased by up to 30.77% and 31.51%, respectively. On the other hand, the random distribution and potential agglomeration of PVA fibers within the HPS matrix can lead to increased air-void formations. This phenomenon raises the volume content of large bubbles and increases the average bubble area and diameter, thereby elevating the pore volume fraction within the 500–1200 μm and >1200 μm ranges. Therefore, these microstructural changes reduce the compactness of the HPS matrix, resulting in a decrease in compressive strength and elastic modulus. The compressive strength exhibited a reduction ranging from 10.44% to 15.11%, while the elastic modulus showed a decrease of between 8.09% and 12.67%. Overall, the PVA-HPS mixtures with different mix proportions demonstrated excellent frost resistance, chloride ion penetration resistance, and carbonation resistance. The electrical charge passed ranged from 133 to 370 C, and the carbonation depth varied between 2.04 and 6.12 mm. Although the incorporation of PVA fibers reduced the permeability and carbonation resistance of shotcrete, it significantly mitigated the loss of tensile strength during freeze–thaw cycles. The findings offer insights into optimizing the use of PVA fibers in HPS applications, balancing enhancements in tensile properties with potential impacts on compressive performance.