The microfiber synthetic leather base pretreated by sulfuric acid was modified by collagen in which the organic phosphine FP was used as a cross-linking agent, for the purpose of increasing the active groups and improving its properties. Compared with the pretreated base, it was found that the amino content in the modified base was two times and the carboxyl content was three times. The water vapor permeability of the modified base increased by 65% and the moisture absorption increased by 181%. It was further found that the tensile strength of the modified base was 19.06 N/mm2, the elongation at break was 54% and the tear strength was 112.34 N/mm. The test results of Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscopy, thermogravimetric analysis and water contact angle showed that the collagen molecules had evenly cross-linked with fiber. The modified base microfiber dispersion was greatly increased, the hydrophility was enhanced and the relative average roughness was decreased. Moreover, modification by collagen also affected the thermal properties of the base.