The rapid development of the Belt and Road Initiative (BRI) has led to severe air pollution dominated by PM2.5 concentrations which can cause a profound negative impact on human health and economic activity. This problem poses a critical environmental challenge to efficiently handling large-scale spatial-temporal PM2.5 data in this extended region. Functional data analysis (FDA) technique offers powerful tools that have the potential to enhance the analysis of spatial distributions and temporal dynamic changes in high-dimensional pollution data. However, modeling the spatial-temporal variability of PM2.5 concentrations by FDA remains unrevealed in the BRI region. To address this research gap, our study aimed to achieve two main objectives: first, to model the spatial-temporal dynamic variability of PM2.5 in 125 BRI nations (1998-2021), and second, to identify the underlying clusters behind the variations. We employed the recently developed functional adaptive density peak (FADP) clustering approach to solve the current problem. The proposed method is based on the joint use of functional principal components (FPCs) and functional cluster analyses. The main results are as follows: (i) The first three FPCs almost captured 99% of the total variations involving all valuable information on PM2.5 concentrations. (ii) PM2.5 pollution was highly concentrated in the developing countries (Pakistan, Bangladesh, and Nigeria) and the developed countries (Arabian Gulf countries: Qatar, United Arab Emirates, Bahrain, Saudi Arabia, Oman), and the least developed countries (Yemen and Chad). (iii) Three optimal clusters were identified and thus classified the PM2.5 into three distinct degrees of pollution: severe, moderate, and light. (iv) Cluster 1 had a severe pollution effect degree with a high rate of change, and it covered the Arabian Peninsula countries, African countries (Cameroon, Egypt, Gambia, Mali, Mauritania, Nigeria, Sudan, Senegal, Chad), Bangladesh, and Pakistan. (v) About 62 BRI countries belonged to cluster 2 showing a light pollution degree with annul average of less than 20 [Formula: see text]; this pointed out that the PM2.5 concentration remains stable in the cluster 2-related countries. The findings of this research would benefit governments and policymakers in preventing and controlling PM2.5 pollution exposure in BRI. Furthermore, this research could pay attention to sustainable development goals and the vision of the Green BRI policy.