For student entrepreneurs with insufficient business experience, they need to hold an open attitude to maintain their competitive advantages in the market and improve their entrepreneurial performance via recruiting talents and creating sales channels using various network resources and advanced IT development technologies. Although field scholars in the world have conducted a lot of research on the evaluation of college students’ innovativeness and entrepreneurship, the differences in study regions, education modes, education concepts, and measurement tools have resulted in large deviations in the evaluation results of different study regions and schools. For this reason, this paper aims to find out the influence mechanism of the improvement of college students’ network ability on the scale of Entrepreneurial Cooperation Network (ECN). At first, the network ability of college students and their fitness degree to harmonious entrepreneurship were measured and analyzed; then, the influence of network ability improvement on ECN scale was studied empirically, and the model regression estimation results were given, which has verified that the psychological quality of student entrepreneurs has a moderating effect on the relationship between their network ability and the scale of ECN they created.