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The present work analyses and prioritises the sustainability barriers in the context of human and organisational (HAO) dimensions in the Indian power sector. A total of eleven barriers were identified through the detailed literature review, the expert’s inputs, and four groups. Further, the decision-making trial and evaluation laboratory (DEMATEL) approach was used to analyse the barriers along with the cause-effect relationship. The study showed that there are five barriers in the cause groups and six in the effect group. The most significant barriers among them are top management/stakeholders support and commitment; lack of green training and awareness; policies and practices for recruitment and selection; performance, appraisal, and reward; environmental knowledge, concern, and attitude; adaptation and linkage of green human resource management (GHRM), and green supply chain management (GSCM). The study emphasised the need to combine efforts from the organisation and government towards sustainability. The managers and decision-makers of the Indian power sector also need to focus on HAO aspects for implementing sustainability in the Indian power sector.