Poly(vinyl alcohol) (PVA)-based films have drawn significant attention owing to their potential applications in various industries. The application of wax to PVA films enhanced their resistance to dissolution and water infiltration. Nevertheless, waxed PVA films often exhibit inadequate mechanical properties owing to crack formation. In this study, we evaluated the impact of glycerol as a plasticizer in varying concentrations of Carnauba wax (CW). The addition of glycerol to the PVA/CW blend led to enhanced mechanical properties compared to the blend without glycerol. The functional group and morphology of the blends confirm glycerol compatibility with PVA/CW films. Glycerol was fully dispersed to form a consistent polymer matrix and equally improved the film’s contact angle. Furthermore, the thermal property from differential scanning calorimetry and thermogravimetric analysis highlights the plasticizing effect of glycerol in PVA/CW films, potentially broadening their use in food packaging and wrapping applications.