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The fabrication process in this study was designed to be both simple and environmentally sustainable. As a result, advanced Gd2NiMnO6 nanofibers (NFs) featuring a unique interface and a highly distinctive external surface were successfully synthesized. This was achieved through a straightforward method that produced a large external surface, constructed via a 3D hierarchical architecture composed of 2D ultrathin nanosheets. By leveraging the potential of dendritic fibrous nanocatalysts, this innovative approach offers promising advancements in the field of green chemistry. Gd2NiMnO6 nanofibers (NFs) were utilized for both static and dynamic CO2 adsorption processes. In this context, Gd2NiMnO6 NFs demonstrated exceptional CO2 adsorption capacity accompanied by remarkably rapid kinetics. The nanofiber morphology of Gd2NiMnO6 provides an optimal outer surface, ensuring efficient CO2 adsorption at each metal site. The nanofiber structure of Gd2NiMnO6 enabled controlled CO2 release, ensuring interaction across the entire surface and facilitating rapid CO2 adsorption kinetics.