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The “last mile” service experience of catering O2O determines user satisfaction and user loyalty of catering O2O platforms. Evaluating user experience of catering O2O distribution link will help catering O2O platforms find problems in the distribution link and provide theoretical support for the improvement of user experience and user satisfaction. From the perspective of distribution link, based on the user experience theory, this paper uses the literature research method, Delphi method, and questionnaire survey method to establish user experience evaluation index system of catering O2O distribution link, including browsing experience, tangible experience, empathic experience, responsiveness experience, reliability experience, and assurance experience 6 factors, and also establishes the BP neural network model. On the basis, the paper selects the data of well-known platform users in East China coastal regions, and trains and simulates the model. The results show that the model can achieve the evaluation of user experience in O2O distribution link. Finally, suggestions for improving user experience in catering O2O distribution link in East China coastal regions are proposed.