The invention belongs to the technical field of hydrogen production materials, and discloses a non-noble metal hydrogen evolution electrocatalyst based on synergistic modification and a preparation method thereof. The catalyst is composed of a metal phosphide active phase, an oxide matrix phase and a carrier, wherein the metal phosphide active phase is dispersedly distributed on the surface of theoxide matrix phase in the form of fine nano-particles, and the oxide matrix phase is loaded on the carrier. According to the invention, the metal phosphide active phase is separated out through a phosphatization reaction and then combined with matrix oxide to construct synergistically catalytic active sites; moreover, the matrix oxide partially reduces the introduced oxygen vacancies, thereby being conducive to improving the electrical conductivity of the matrix material; in addition, when being heated, the precursor material generates a large amount of nano-pores due to dehydration or deamination, thus further improving the mass transfer performance of the catalyst while providing more active sites. Therefore, three factors intrinsic activity, number of active sites and electrical conductivity can be optimized simultaneously. The non-noble metal hydrogen evolution electrocatalyst based on synergistic modification is close to the noble metal Pt catalyst in comprehensive catalytic properties.