Nanostructure design and in situ transmission electron microscopy (TEM) are combined to demonstrate Sb-based nanofibers composed of bunched yolk-shell building units as a significantly improved anode for potassium-ion batteries (PIBs). Particularly, a metal-organic frameworks (MOFs)-engaged electrospinning strategy coupled to a confined ion-exchange followed by a subsequent thermal reduction is proposed to fabricate yolk-shell Sb@C nanoboxes embedded in carbon nanofibers (Sb@CNFs). In situ TEM analysis reveals that the inner Sb nanoparticles undergo a significant volume expansion/contraction during the alloying/dealloying processes, while the void space can effectively relieve the overall volume change, and the plastic carbon shell maintains the structural integrity of electrode material. This work provides an important reference for the application of advanced characterization techniques to guide the optimization of electrode material design.