The interactive development of economic globalization, informatization, marketization, and urbanization has reshaped the urban commercial landscape and society, and poses new requirements for the business environment. New commerce forms that are based on information technology and electronic payment and integrate online and offline forms are growing rapidly in China. However, the relationship between new commerce forms and the business environment has not received sufficient academic attention. Using 29 major cities in China, this paper constructs a new business index system consisting of the following six sub-indexes: the characteristic hotels index, the Starbucks index, the Freshhema index, the concept bookstores index, the smart convenience stores index, and the healthcare and medical examination index. The entropy coupled with the Technique for Order Preference by Similarity to an Ideal Solution (TOPSIS) method was used for quantitative evaluation of urban new business vitality. We found that the Freshhema index and smart convenient store index are the two most important evaluation factors. The relationship between the new business index and the business environment was examined through multiple linear regression (MLR) and Gaussian process regression (GPR) analysis. We found that the MLR is not a valid model, and instead, the nonlinear GPR model has good explanatory power for this relationship. The results show that human capital has a more important effect than the economic development level on business vitality. The rise and development of new commercial forms depend on the innovation and optimization of the business environment.