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. The assessment results show that Shenzhen, Beijing, Hefei, Shanghai, Hangzhou are the 5 cities which perform better in the city readiness assessment. Purchasing subsidies, quantity of electric vehicles per resident, quantity of cumulative charging times per vehicle, total infrastructure investment per resident, quantity of charging piles per vehicle, quantity of cumulative electricity per vehicle and quantity of operators are the 6 biggest indicators impacting on the level of city readiness system. To promote the electric vehicle commercialization, the key issues of improving the charging network construction, developing reasonable charging and service price and raising consumer awareness need to be solved.