This thesis employs statistical learning technique to analyze, predict and solve the fixed charge network flow (FCNF) problem, which is common encountered in many real-world network problems. The cost structure for flows in the FCNF involves both fixed and variable costs. The FCNF problem is modeled mixed binary linear programs and can be solved with standard commercial solvers, which use branch and bound algorithm. This problem is important for its widely applications and solving challenges. There does not exist a efficient algorithm to solve this problem optimally due to lacking tight bounds. To the best of our knowledge, this is the first work that employs statistical learning technique to analyze the optimal flow of the FCNF problem. Most algorithms developed to solve the FCNF problem are based on the cost structure, relaxation, etc. We start from the network characteristics and explore the relationship between properties of nodes, arcs and networks and the optimal flow. This is a bi-direction approach and the findings can be used to locate the features that affect the optimal flow most significantly, predict the optimal arcs and provide information to solve the FCNF problem. In particular, we define 33 features based on the network characteristics, from which using step wise regression, we identify 26 statistical significant predictors for logistic regression to predict which arcs will have positive flow in the optimal solutions. The predictive model achieves 88% accuracy and the area under receiver operating characteristic curve is 0.95. Two applications are investigated. Firstly, the predictive results can be used directly as component critical index. The failure of arcs with higher critical index result in more cost increase over the entire network.