Summary: Measuring the sustainability performance of supply chains is fundamental to sustainable supply chain management. Sustainability performance is usually evaluated from multiple aspects within the triple bottom line framework. With globalization, supply chains have also been characterized by the complex and global natures. Ignoring the multidimensional and transnational features imposes challenges on the performance assessment of global supply chains (GSCs). To resolve this issue, we propose an input-output modeling approach based on the multi-region input-output (MRIO) model and the data envelopment analysis (DEA) technique, which is able to account for the multidimensional characteristic of supply chains in a global context. Two indices are introduced to measure the status and evolvement of environmental sustainability performance of GSCs. We apply the proposed approach to empirically examine the environmental performance of GSCs of the manufacturing sectors in 16 major economies during 2005–2014. The average environmental inefficiency of the economies was considerable, and roughly 40% of the pollution could potentially be reduced along GSCs. Overall the environmental performance of GSCs averagely rose by 20.6% during the study period with fluctuations and regional/sectoral heterogeneities observed.