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Through exploration and exploitation of new knowledge emergence, the collective intelligent decision-making (CID) level of Web-of-Cells (WoC) proposed by ELECTRA will be dramatically improved. For this purpose, we thoroughly investigate complex network theory and modeling methods for WoC with cyber-physical-social systems (CPSS). WoC is a new intelligent dispatching framework characterized by weak centralization, self-organization coupling, high independence, efficient coordination, and autonomous learning. Based on these characteristics and actual engineering demands, in this paper, we adopt complex network theory, parallel machine learning, and multi-agent stochastic game theory to address three basic scientific issues in WoC dispatching and control: how to build a complex network model for WoC with CPSS to stimulate new knowledge emergence; how to analyze the evolution structure stability and operation stability during this knowledge emergence process; and how to use the emerged new knowledge to achieve cell autonomy and system-wide coordination based on independent and CID, respectively. Finally, we conduct some explorations and make a prospect for WoC. The biggest innovation of this paper lies in thoroughly investigating how to fully stimulate and utilize new knowledge emergence from WoC to greatly improve its CID level of dispatching and control. This will be of great significance to the development of new-generation power system smart dispatching in the future.