Loess has high water sensitivity and exhibits poor characteristics such as weak cementation and high porosity. Under heavy rainfall, loess fill slopes are prone to erosion and landslides, posing serious threats to public safety and property. In light of these serious threats, this study employed the method of spraying polyvinyl alcohol (PVA) solution to improve loess fill slopes and systematically examine its protective effects. Through field investigations and combined laboratory and outdoor tests, this study comprehensively evaluated the mechanical properties, anti-aging and anti-erosion performance of loess after PVA solution spraying. Scanning electron microscopy was used to reveal the mechanism of PVA action at the microscopic level. The results showed that after treatment with PVA solutions of varying concentrations, the mechanical properties of loess samples were significantly enhanced, while also exhibiting excellent anti-aging and water resistance performance. Additionally, PVA-treated loess fill slopes exhibited excellent rain erosion resistance. A microscopic structural analysis showed that PVA fills the internal pores of loess, strengthens inter-particle bonding, and uses its hydrophobic groups’ water-repellent action to effectively enhance slope stability and erosion resistance. In conclusion, PVA treatment not only significantly enhances the protective effects of loess fill slopes but also holds important value in improving soil sustainability and environmental protection.