In the present paper, the thermal durability of polyvinyl alcohol fibers (PVA) was studied after fiber samples had been subjected to temperatures ranging from 90°C to 250°C. Residual mechanical properties, such as tensile strength, elastic modulus and elongation at break, and physical properties, such as density were determined. Weibull statistics were used to quantify the degree of variability in fiber strength, at the different temperature. In addition, thermal analysis of PVA fibers were carried out employing thermogravimetry and differential scanning calorimetry up to the temperature of 800°C. SEM analysis of heated and unheated samples had been carried out in order to allow the identification of the changes in the microstructure of the fibers. The degradation process of PVA fibers manifests itself in a significant loss of mass, stiffness and strength of the fibers, which is progressive with increasing temperature. Thermal analysis has shown that the melting point of PVA fibers begins at approximately 200°C and thermal degradation initiates at about 239ºC. However, progressive loss in tensile strength and elastic modulus was observed starting at a temperature as low as 90°C, due to glass transition temperature of PVA fibers at approximately 66°C. At 220°C, the elastic modulus and strength were reduced at about 45% and 52%, respectively, when compared with respective values of unheated samples. With regards to Weibull modulus, the statistical parameter did not exhibit significant influence on temperature for samples heated up to 145°C, which ranged from 23.4 to 28.8. However, samples heated to 220°C showed a sudden reduction in Weibull modulus to 8.6, indicating that a significant change occurred in the populations of fracture inducing flaws at this temperature level, which clearly affect the tensile strength and Weibull modulus.