Based on experimental results of strength and deformation under uniaxial compression, the influences of PVA fiber content by volume, fly ash and silica fume content on compression performance of PVA FRCC with high toughness were investigated. The compressive strength, elasticity modulus, Poissons ratio and the axial compressive stress strain curves were obtained. According to test results, the relationship formula between cubic compressive strength and axial compressive strength, and between elasticity modulus and compressive strength were established. Using electron microscope, the microstructure of PVA FRCC with high toughness was also observed. Furthermore, according to the complete test curves, an equation for the constitutive relationship of PVA FRCC with high toughness was deduced under uniaxial compression, which is the theoretical basis on nonlinear finite element analysis and structure design.