With the in-depth development of digitalization and globalization, the competition and cooperation of network virtual organizations in the industrial economy have become increasingly frequent and complex. In this context, the traditional decision-making mechanism has been unable to adapt to the dynamic and changing market environment, and it is unable to effectively balance the interests of all parties and achieve the optimal allocation of resources. This paper focuses on the decision-making difficulties of network virtual organizations in the industrial economy. Based on the theoretical framework of game theory, this paper designs a scientific decision-making mechanism, selects a suitable game algorithm, and constructs a network virtual organization model to deeply analyze its decision-making behavior in competition and cooperation. This paper first systematically designs the decision-making mechanism and clarifies the decision-making elements and processes; secondly, it introduces the game algorithm suitable for this scenario in detail to provide theoretical support for decision-making; finally, it constructs a network virtual organization model to simulate the actual decision-making process. Through simulation experiments and case analysis, at the strategic quality level, the introduction of the Shapley value allocation mechanism in cooperative decision-making has increased member satisfaction by 15%-20%, effectively curbing the “free-riding” phenomenon; the stable strategy based on evolutionary game in competitive decision-making has reduced the volatility of returns by 25%, verifying the effectiveness and feasibility of the proposed decision-making mechanism and model, which can significantly improve the decision-making efficiency and benefits of network virtual organizations in industrial economic activities, and provide new ideas and methods for the scientific decision-making of network virtual organizations in industrial economic competition and cooperation.