Improving the accessibility of coal transportation is a crucial issue for energy security, national defense, and livelihoods. In this study, a method to evaluate the performance of the port-centric coal transportation chain (PCTC), which is a crucial part of the international coal production and delivery process, is proposed. After analyzing the features of the port-centric coal transportation chain, a practical accessibility evaluation model is established based on the gravity model. Both the foreland and hinterland features are considered in the model. Based on the features of coal transportation, the concept of port operational adaptability is introduced to indicate the port’s ability to manage a fluctuating irregular workload. Moreover, environmental factors, including transportation emissions and dust pollution, are included in the evaluation system. Based on real data collected from China’s north-south coal transportation corridor, a case study presents the implementation of this comprehensive evaluation system in practice. This evaluation system enables us to determine the vulnerable areas in the coal maritime transportation network and provides a decision-making basis for both shippers and port owners.