Pavement straw composite fibers (PSCF), a new material, were independently invented and developed by blending agriculture waste straw and modified bentonite, as showed in this paper. The chemical corrosion properties of PSCF in different pH values were test in microscale, and digital imaging processing technology was adopted to analyzing quantitatively the physical and mechanical properties, including particle area, pores connectivity rate and compressive strength, before and after PSCF were corroded. Research results show that the particle area of acidified PSCF is smaller than that of alkalized PSCF, however, the fractal dimension of acidified PSCF is bigger than that of alkalized PSCF. The change of PSCF microstructure has significant effect on its macromechanics properties. The compressibility of acidified PSCF was obviously bigger than that of alkalized PSCF, so the strength of acidified PSCF decreased significantly with the acidifying time increasing. The main reason was gradually decreasing of the particle area, decreasing of the fractal dimension and the loose tendency of fibers particle distribution. The interaction between mineral composition of PSCF and hydrochemistry solution was the basic factors determining straw structural characteristics, and the physical and mechanical properties of PSCF were affected by its structural characteristics. The main process was that mineral compositions of PSCF were cemented by the corrosive action of hydrochemistry solution, or some compositions were dissolved and precipitated, the porosity and particle area of PSCF, the arrangement pattern of soil particles as well as other microstructures changed. And deformation properties of PSCF changed correspondingly with the change of PSCF structure shape. Moreover, the constitutive model of PSCF with effect of acid and alkali was presented according to test data of digital image. It provided reliable techniques to quantitatively evaluate the pavement performance of PSCF in micro and macro scales. Furthermore, the chemical corrosion theory was improved, and the reference for constitutive model research was provided.