The unemployment problem of college students in China has drawn much attention from academics and society. Using the 2011 College Student Labor Market (CSLM) survey data from Tsinghua University, this paper estimated the effects of college quality on initial employment, including employment status and employment unit ownership for fresh college graduates. The propensity score matching method was employed to account for the potential endogeneity of elite college attendance. The empirical evidence suggested that students who attended Project 985 colleges were more likely to find jobs immediately after college graduation. Moreover, students graduated from Project 211 universities gained a competitive edge by entering into public working sectors, such as the government or state-owned enterprises (SOEs), compared with students from non-elite colleges. The results imply the students who graduated from non-elite universities faced labor market segmentation. They not only had obstacles in finding jobs, but also ended up in the secondary labor market.