With regard to the network optimization problem of online supply chain based on online to offline, the super network theory is used to construct the model of the supply chain. Then the independent optimization is modeled based on the single supply chain member, and the integrated optimization is modeled based on all the supply chain members according to the optimization theory of the variational inequality. Further more, the two models are compared by simulation application. Finally, the paper concludes the supply chain can gain more economic benefit and bring win-win effect to all its members if they invest on the online to offline operation on the condition that all its members' profit is maximized.