Sustainable zinc-air batteries (ZABs) are considered promising energy storage devices owing to their inherent safety, high energy density, wide operating temperature window, environmental friendliness, etc., showing great prospect for future large-scale applications. Thus, tremendous efforts have been devoted to addressing the critical challenges associated with sustainable ZABs, aiming to significantly improve their energy efficiency and prolong their operation lifespan. The growing interest in sustainable ZABs requires in-depth research on oxygen electrocatalysts, electrolytes, and Zn anodes, which have not been systematically reviewed to date. In this review, the fundamentals of ZABs, oxygen electrocatalysts for air cathodes, physicochemical properties of ZAB electrolytes, and issues and strategies for the stabilization of Zn anodes are systematically summarized from the perspective of fundamental characteristics and design principles. Meanwhile, significant advances in the in situ/operando characterization of ZABs are highlighted to provide insights into the reaction mechanism and dynamic evolution of the electrolyte|electrode interface. Finally, several critical thoughts and perspectives are provided regarding the challenges and opportunities for sustainable ZABs. Therefore, this review provides a thorough understanding of the advanced sustainable ZAB chemistry, hoping that this timely and comprehensive review can shed light on the upcoming research horizons of this prosperous area.