China’s mass entrepreneurship and innovation policy have inspired many individuals to join incumbent agglomerations to supplement their resource insufficiency. Based on the ties of kinship and township relations among a typical agglomeration, this paper explored the individuals’ preferential attachment rules and analyzes the network properties. The main findings included: self-employment agglomeration with given preferential attachment rules has a large average degree; this kind of network is scale-free, and it follows power-law degree distribution; clustering coefficient is very large; the average path length is short and it follows a power-law distribution. Our findings demonstrated that this typical self-employment agglomeration is a kind of complex network. We also discussed the mechanism of complex network’s advantages on self-employment activities.