This paper uses complex network analysis to research the internal structure of the relevant factors affecting employee green behavior (EGB) and apply to actual business operations based on the background of corporate sustainable development. The analysis is based on social network analysis (SNA) to find important factors affecting employee green behavior (EGB), and use cluster analysis to construct cohesive subgroups of influencing factors. Besides, further use cohesive subgroups to form an evaluation index system by a specific form- employee green behavior ability (EGBA), and combined VIKOR and Pythagorean Fuzzy Number (PFN) model to evaluate EGBA in the reality. The influencing factors of EGB mainly include 17 items, such as Support green behavior, Job satisfaction, Target consistency, living environment, Perceive green self-efficacy, etc. Among them, the degree of target consistency, the proportion of green knowledge, skills shared among organizations, the quality of employees' personal traits, Individual education level and self-control ability have the greater impact. Further studying its inherent similarity, we found that these factors can be summarized into four major subgroups, of which subgroup four has the deepest influence. In order to present the abstract concept of EGB, we find it can be used in conjunction with specific evaluation methods through build an index system of the employee green behavior ability (EGBA). It is effective to grasp the green behavior and practical to the company. The research helps to expand the in-depth study of the influencing factors abut EGB, and helps managers to evaluate EGBA or promote the implementation of EGB in the organization for the company's sustainable development.