The street network is considered the skeleton of the city structure; it determines the efficiency and productivity of the city in that it acts like blood vessels transporting people, goods, and information. The relationship between street networks and economic development is an important research topic in urban geography. In recent years, complex network theory has been successfully used for understanding the characteristics of street network structure. However, researchers lack an analytical framework and methods for studying the relationship between the morphological structure of urban streets and the economic development level of cities. Accordingly, this paper proposes a methodological framework for first, quantitatively characterizing the urban morphological structure based on open street network data, and second, exploring the relationship between the morphological structure of the urban street and the urban economic development level. The proposed methodology was applied to 31 provincial capital cities in China. The results indicate that urban morphological structure can be quantitatively described by betweenness and closeness centrality extracted from street networks. Cities with similar structures have similar levels of economic development. Moreover, the results suggest a significant positive correlation between street network betweenness centrality Gini coefficients and cities’ economic development levels, indicating that the street network may affect city productivity. This study makes two major contributions to the scholarly literature. Methodologically, the proposed framework provides technical and methodological support for a better understanding of the relationship between cities’ economic development and urban street structure. Empirically, the demonstrated case study may guide decision-making involving regional development and the optimization of urban space.