This study investigates how CEO succession involving changes in academic experience influences firm-level AI innovation outcomes. Drawing on insight from upper echelons theory and the knowledge-based view, we examine two distinct transitions: from non-academic to academic CEOs (NACA-to-ACA) and from academic to non-academic CEOs (ACA-to-NACA). We propose that NACA-to-ACA successions positively affect AI innovation, driven by knowledge-oriented leadership and strategic alignment with exploratory innovation goals. Conversely, ACA-to-NACA transitions negatively impact innovation by disrupting established knowledge systems. This study further identifies moderating factors—TMT AI orientation, TMT power with digital expertise, and regional AI knowledge ecosystems—that amplify or buffer these effects, underscoring the importance of organizational and contextual resources. Using a sample of 3,096 CEO succession events across 1,864 listed firms in China between 2013 and 2023, we find evidence largely supporting our arguments.