In this paper, we select some indexes and establish a model to evaluate the coupling state by applying the gray relation analysis. We choose seven cities in Guangdong as samples, which include Guangzhou, Shenzhen, Foshan, Dongguan, Zhongshan, Zhuhai and Huizhou, and carry out an empirical study on the coupling state of city brand economy and market environment with the model. The result shows that the most important factor influencing Guangdong city brand economy in Shenzhen, Foshan, Dongguan and Zhongshan is the enterprise environment, followed by the open environment, the human environment, the science and technology environment and the institutional environment. The cultural environment is first factor influencing the Guangzhou’s brand economy in all factors, followed by the enterprise and the capital environment. We suggest that the empirical analysis method for coupling state between the city brand economy and the market environment facilitates the promotion of the coordinated development between the market environment and city brand economy.