The realm of Artificial Intelligence (AI)'s impact on our lives is far reaching - with AI systems proliferating high-stakes domains such as healthcare, finance, mobility, law, etc., these systems must be able to explain their decision to diverse end-users comprehensibly. Yet the discourse of Explainable AI (XAI) has been predominantly focused on algorithm-centered approaches, suffering from gaps in meeting user needs and exacerbating issues of algorithmic opacity. To address these issues, researchers have called for human-centered approaches to XAI. There is a need to chart the domain and shape the discourse of XAI with reflective discussions from diverse stakeholders. The goal of this workshop is to examine how human-centered perspectives in XAI can be operationalized at the conceptual, methodological, and technical levels. Encouraging holistic (historical, sociological, and technical) approaches, we put an emphasis on "operationalizing", aiming to produce actionable frameworks, transferable evaluation methods, concrete design guidelines, and articulate a coordinated research agenda for XAI.