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A free-standing Si@Co 9 S 8 CF electrode with excellent rate capability and cycling performance was obtained by electrospinning, vulcanization, and carbonization processes as high-performance anode for Li-ion batteries. [Display omitted] • Si@Co 9 S 8 CF films are explored by electrospinning, vulcanization and carbonization. • The yolk-shelled Si@Co 9 S 8 can remarkably alleviate the volume expansion. • The introduction of CFs can improve the electrical conductivity of the electrodes. • The free-standing anode avoids the conventional process of electrode preparation. Silicon-based (Si-based) materials have aroused extensive attention owing to their ultra-high theoretical specific capacity, while the huge volume expansion and inferior electronic conductivity have impeded their practical application in lithium-ion batteries (LIBs). Rational structural design has been regarded as a fascinating strategy, especially for yolk-shell structures. Herein, Si nanoparticles (Si NPs) were encapsulated in ZIF-67 metal–organic frameworks to obtain Si@ZIF-67 particles, which were wrapped in one-dimensional carbon fibers (CFs) by simple processes of electrospinning, vulcanization and carbonization to obtain a free-standing Si@Co 9 S 8 CF electrode. The yolk-shelled Si@Co 9 S 8 particles could remarkably ameliorate the volume variation of Si materials during the lithiation/de-lithiation cycling and the introduction of CFs endowed an efficient one-dimensional electronic pathway accurately to improve the conductivity of composite materials. In addition, it was not negligible that the as-obtained Si@Co 9 S 8 CF films could be as a self-supporting electrode, which avoided the traditional cumbersome procedure of the electrode preparation. The resulting composite electrodes possess an excellent rate performance and an ultra-stable cycling lifespan. We hope this work can provide some novel insights for the development of the self-supporting Si-based electrode materials. [ABSTRACT FROM AUTHOR]