As an important indicator for measuring the quality of business environment of different countries, ease of doing business (EDB) issued by the World Bank (WB) provides an important reference for investors in making decisions on transnational investment. The calculation method for EDB issued by the WB is improved using a technique for order preference by similarity to an ideal solution (TOPSIS) method based on Mahalanobis distance. Based on various indicator data in 2019, business environments in 121 countries participating in “the Belt and Road Initiative (BRI)” were empirically analysed and compared through such models. The result showed that TOPSIS method based on Mahalanobis distance can more fully utilise information and take the effect of negative ideal points into account. Therefore, compared with ranking method by the WB, TOPSIS method based on Mahalanobis distance is more applicable for ranking BRI countries. The ranking results indicated significant geographical characteristics. The EDB rankings obtained through the WB overestimate the business environments of countries in Central and Eastern Europe while underestimate those in Southeast Asia, Africa, etc.