This study demonstrates the application of Si/C composite fibers as anode materials for all-solid-state lithium-ion batteries. Using polyacrylonitrile as the carbon precursor, Si/C fibers were prepared through electrospinning and subsequent heat-treating processes. To investigate the correlation between fiber diameter and electrochemical performance, we prepared three electrodes (A, B, C), containing Si/C fibers with similar to 2 mu m, similar to 1 mu m and similar to 0.1 mu m diameters, respectively. Our results revealed that although the composition of all three electrodes was nearly the same, the Si/C fiber based electrodes exhibited better capacity retention when their fiber diameters were smaller. Normalized to the total mass of electrode composite, the solid-state half-cell prepared with the smallest diameter (similar to 0.1 mu m) Si/C fibers achieved a reversible specific capacity of similar to 700 mAh g(-1) (normalized to electrode mass) over 70 cycles. We believe that this report can serve as an informative approach toward the utilization of electrospun Si/C fibers as anode materials for all-solid-state lithium-ion batteries. (C) The Author(s) 2018. Published by ECS.