This study investigates the influence of organizational psychological capital (OPC) on corporate environmental, social, and governance (ESG) practices, highlighting a relatively overlooked aspect in existing studies, and examines the moderating effect of chief executive officer (CEO) power on this relationship. Using a dataset of 1659 firm‐year observations from FTSE 350 firms across the years 2012–2021 and applying natural language processing (NLP) techniques, our findings reveal that higher levels of OPC are linked to a stronger commitment to ESG initiatives. However, this positive association is tempered by CEO power, which negatively moderates the relationship. Furthermore, our analysis shows that OPC not only enhances ESG performance but also positively influences financial performance and the core ESG pillars. These results, validated through rigorous robustness checks, offer significant insights for stakeholders and policymakers in the realm of corporate governance.