In this study, the effect of polyvinyl alcohol (PVA) fiber volume fraction on the pullout behavior of structural synthetic fiber in hybrid structural synthetic fiber and PVA fiber cement composites are presented. Pullout behavior of the hybrid fiber cement composites and structural synthetic fiber were determined by dog-bone bond tests. Test results found that the addition of PVA fiber can effectively enhance the structural synthetic fiber cement based composites pullout behavior, especially in fiber interface toughness. Pullout test results of the structural synthetic fiber showed the interface toughness between structural synthetic fiber and PVA fiber reinforced cement composites increases with the volume fraction of PVA fiber. The microstructural observation confirms the incorporation of PVA fiber can effectively enhance the interface toughness mechanism of structural synthetic fiber and PVA fiber reinforced cement composites.