The aim of this study was to examine effects of polyvinyl alcohol (PVA) on buck semen quality. Seventy-five ejaculates were collected and diluted in Tris-egg yolk extender containing one of three PVA co-polymers of 9, 18 and 100 kDa. Five different concentrations 0.001, 0.01, 0.1, 1 and 2% of the PVA co-polymers were added to the extender with respected to the decreasing glycerol concentrations of 5, 4, 3, 3, 2% respectively. Following freeze-thaw, sperm motility, viability, acrosome-intact spermatozoa and mitochondrial membrane potentials were analysed. During freezing, sperm seeding temperature were recorded with a cryo-thermometer. PVA 2% glycerol group gained 8.2 ± 1 °C latent heat plateau difference comparing to control. Highest motility was found in PVA 18 kDa with regardless of the dosage (P < 0.001). All PVA copolymers gained higher motility independently in all other dosage groups (except PVA 2%) comparing to control (P < 0.001). Live spermatozoa rate between treatment groups were statistically insignificant (P = 0.953), however, when moribund sperm were gated out PVA 9 induced better protection with respect to other groups (P < 0.05). Intact acrosome rate was statically higher in PVA groups (P < 0.002) and subgroups (P < 0.001). Mitochondrial membrane potential was higher in all experimental groups comparing to control group (P < 0.001). PVA co-polymer concentrations of 0.01, 0.1, 1 and 2% v/v (PBS: PVA) decreased the concentration of glycerol required for freezing in a 100 ml volume by 0, 1, 2, 2, and 3% v/v from the control dose (5%), respectively. In conclusion, synthetic PVA-derived ice blocking agents offer new opportunities for improving the post-thaw buck sperm quality.