As organizations increasingly prioritize sustainability and the management of ESG (Environmental, Social, and Governance) risks, understanding the mechanisms that enhance sustainability performance and stakeholder perceptions becomes critical. The rise in the number of companies creating the role of the Chief Sustainability Officer (CSO) is a key indicator of this shift. However, the impact of the role on the sustainability performance of the firm is still ambiguous. This study investigates why some firms with CSOs have different sustainability outcomes than others that are similar on various dimensions. We explore the key factors related to firm governance and structure around the CSOs and examine the variance in the performance implications for sustainability. Through an inductive approach, this research begins with 40 interviews and progresses to a detailed analysis and comparison of four Fortune 500 companies as a multiple-case comparative study. The study aims to uncover why some CSOs are more effective than others in the same role in relation to the sustainability performance of the firm. Findings suggest that high-performing firms on sustainability metrics typically position their CSO close to the CEO, involve the CSO in critical strategic decisions, engage with external stakeholders through collaborations and engage in dialogue with policymakers. We also find that high-performing firms on sustainability appoint CSOs with no expertise in sustainability, but rather a background in leadership and strategy positions. This research highlights the differences in sustainability performance among firms with similar ESG risk exposures, emphasizing the role of governance and executive positioning in achieving superior sustainability outcomes.