The impact of corporate governance mechanisms has been examined directly and independently, considering that such characteristics compete to explain environmental, social, and governance (ESG) performance. However, the nexus may be more complex than that suggested by most scholars, and more research is needed. This study applied a fuzzy-set qualitative comparative analysis to a sample of Spanish-listed companies in 2018–2020 to explore how good governance practices interact with CEO profiles to promote corporate sustainability practices. Our analysis discovered the importance of establishing sustainability committees and identified five pathways shaping governance practice bundles. Specifically, listed companies with a high code of good governance (GGC) compliance and a sustainability committee improve high ESG performance globally and for each ESG dimension. Furthermore, the effect is more relevant than the effect of the CEO profile, requiring either CEO duality (pathway 1) or extended CEO tenure (pathway 2). Concurrently, findings indicate three CEO profile configurations for GGC-neutral firms, providing companies with more flexibility in CEO selection. Two suggest that younger CEOs with longer tenure tend to be more motivated to engage in the G and S pillars (pathways 3 and 5). The third indicates that CEOs of older age and early tenure improve the E pillar (pathway 4).