This paper adopts the method of synergetic theory fused with a random matrix to conduct in-depth research and analysis on the innovation and entrepreneurship education of college students, discusses the existing problems, and develops ways of college students’ entrepreneurship education from the perspective of synergetic students. The development history of entrepreneurship education of college students is explained, the development of entrepreneurship education in case institutions is introduced and the synergistic subjects of college students’ entrepreneurship education are introduced, and the necessity of carrying out college students’ entrepreneurship education is analyzed. The mechanism of cooperation mechanism of total budget management is studied from three perspectives of organizational cooperation, information cooperation, and resource cooperation respectively. From the perspective of internal and external collaborative training platforms, the idea of improving college students’ entrepreneurship education is put forward. Among them, colleges, teachers, and college students form an internal system for the development of entrepreneurship education, and the three are synergistically dependent on each other and influence each other. Then, the problems in entrepreneurship education are analyzed, including weak teachers in entrepreneurship education in colleges and universities, systematic and professional entrepreneurship education to be improved, insufficient internal drive-in entrepreneurship education in colleges and universities, and insufficient initiative of college students to participate in entrepreneurship education. Finally, the ways to solve the existing dilemmas of entrepreneurship education of college students from the perspective of synergism are proposed, including improving the initiative of college students and the atmosphere of social and cultural environment, constructing internal and external platforms for entrepreneurship education of college students, and evaluating and giving feedback to entrepreneurship education of college students so that colleges and universities can better promote and carry out entrepreneurship education.