Social e-commerce is an emerging e-commerce mode in response to the upgrading of consumption, which has become an important engine for the development of the digital economy. Knowledge transfer and sharing play vital roles in improving the competitiveness and the sustainability of social e-commerce platform enterprises. However, academic research on knowledge transfer for the social e-commerce platform enterprise’s operation team remains deficient. To help social e-commerce platform enterprises to improve performance and better seek survival and sustainable development, this paper constructs a knowledge transfer model for the social e-commerce platform enterprise’s operation team, in the self-centered sustainable ecological business mode, from the relationship between intra-organizational operation knowledge transfer and cross-organizational knowledge sharing for value co-creation, and explores knowledge transfer behaviors from the perspective of complex network-based evolutionary game under strategy imitation preferences. Simulation results indicate that relationships among knowledge transfer cost, knowledge synergy benefit, cross-organizational value co-creation benefit rate, and reward and punishment, along with strategy imitation preferences, significantly impact knowledge transfer behaviors of the social e-commerce platform enterprise’s operation team. When all the members of the social e-commerce platform enterprise’s operation team prefer to imitate the knowledge transfer strategies of the operation members with smaller knowledge transfer costs, the operation team is more likely to show a high proportion adopting the transfer strategy, requiring low knowledge synergy coefficient, reward, punishment, and cross-organizational value co-creation benefit rate to achieve stable and sustainable knowledge transfer. Conversely, the operation team is more likely to show a low proportion adopting the transfer strategy, requiring high knowledge synergy coefficient, reward, punishment, and cross-organizational value co-creation benefit rate to achieve stable and sustainable knowledge transfer. This study has significance as a guide for social e-commerce platform enterprises in deploying the self-centered sustainable ecological business mode.