In recent years, the “Belt and Road Initiative” (BRI) promoted by the Chinese government has attracted a significant amount of international trade and transnational investment and other businesses. Accordingly, country risk assessment should be granted priority in the decision-making process for these projects. Based on a comprehensive consideration of important relevant countries and the availability of data of countries along the BRI, this paper uses data from 49 countries along the BRI between 2014–2019 and establishes a national risk-evaluation system for the BRI from four dimensions (i.e., political, economic, social, and investment). This paper adopts the Grey correlation analysis based on the Technique for Order Preference by Similarity to Ideal Solution (Grey-TOPSIS) method to identify and evaluate the risk of countries along the BRI. Geographic Information System (GIS) maps are drawn according to the criteria for classifying the five risk levels to show the rank of the four aspects of risk scores along the BRI in 2019 and the rank of overall country risk scores during the period 2014–2019. The proposed conclusion and policy implications can help the Chinese government and companies to make informed decisions and minimize potential risks.