To improve the utilization of crop straws as a resource and the compatibility between straw fibers and cement-based materials, the hydration of modified straw fiber cement-based composite (SFCC) was studied. e structural characteristic of SFCC was investigated by FTIR, SEM, and XRD. e results show that the setting time of several modified straw fiber SFCC pastes was shorter than that of the unmodified straw fiber SFCC paste, and the best method of fiber modification to improve the setting time of the SFCC paste is Na 2 O·nSiO 2 treatment. e recommended fiber modification method for improving the compatibility between straw fibers and cement-based materials is alkali modification, followed by pure acrylic emulsion modification and Na 2 O·nSiO 2 modification. To improve the strength of SFCC, the straw fiber should be modified by alkali, followed by pure acrylic emulsion and Na 2 O·nSiO 2 modification and the method of water modification is also recommended. e phase types and relative contents of crystalline hydration products mixed with the modified straw fiber SFCC are significantly higher than those of the unmodified fiber SFCC. e fiber treatment method that was most helpful to increase the structural density of hydrates of SFCC was alkali treatment and pure acrylic emulsion treatment, followed by Na 2 O·nSiO 2 treatment.