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The Chinese government initiated the “Ten Cities, Thousand Vehicles” program for electric vehicles from the year of 2009 to 2012. The demonstration results indicate that an integral city readiness system is required in the promotion of electric vehicles, including the government policies, charging infrastructure, after-sales service, business models and consumer awareness. Through the analysis of related literature and summary reports from 25 demonstration cities, a partial least squares (PLS) path model with 5 major factors and 13 observation indicators was developed to assess the city readiness of electric vehicle adoption. The 5 factors consist of government policies and investment, charging infrastructure construction and operation, business models and maintenance service system, consumer awareness education, operation scope and environmental benefits. Based on the PLS results, 25 cities are classified into 6 groups with the clustering analysis model.