The global pharmaceutical industry faces a pressing need to prioritize sustainability in its supply chain as it holds the potential to significantly influence its profitability and growth. Leveraging Industry 5.0 technologies can help to enhance sustainability in the pharmaceutical supply chain. Despite its evident benefits, organisations tend to be hesitant to adopt these technologies due to various reasons. This study aims to identify the barriers to Industry 5.0 adoption in the Pharmaceutical Supply Chain to strengthen sustainability and explore the inter-relationships among these barriers. Through an extensive literature review followed by interviews with pharmaceutical supply chain experts, this research identifies ten key barriers to Industry 5.0 adoption in the PSC. Employing the DEMATEL approach, the study explores the inter-relationships among these barriers. Notably, ‘Lack of standardization and fair benchmarking practices’, ‘Insufficient or weak IT infrastructure’ and ‘Risk in data sharing’ emerge as critical causal barriers. The elimination of these three barriers holds the potential to remove a significant number of other barriers to Industry 5.0 adoption in the PSC, thereby fostering sustainability. The findings of this paper could support various pharmaceutical organizations, government bodies and industry associations in formulating policies for the adoption of Industry 5.0 in the pharmaceutical supply chain ultimately enhancing sustainability practices in the pharmaceutical industry.