This study addresses the application of polyvinyl alcohol (PVA) fibers to improve the performance of lightweight cement composites with pozzolans. Blended cement mixes based on expanded glass granules were modified with PVA fibers (Type A: Ø40 m, L = 8 mm and Type B: Ø200 m, L = 12 mm). The following research methods were used to analyse the effect of the fibers on the structure of cement matrix and physical-mechanical properties of lightweight composite: SEM, XRD, DTG, calorimetry tests, and standard test methods of physical and mechanical properties. Results from the tests showed that a denser layer of hydrates was formed around the PVA fiber and the amounts of portlandite, CSH, and CASH formed in the specimens with PVA were found to be higher. PVA fibers of Type A accelerated hydration of the cement paste, slightly increased the compressive strength of the lightweight composite, but had no significant effect on the values of density, ultrasonic pulse velocity and flexural strength. The shrinkage of cement composite was significantly reduced using both types of PVA fiber and both types of PVA fibers increased the fracture energy of lightweight cement composite with expanded granules.