Applications of transition metal dichalcogenides as Li-ion battery electrode have been of great interest because of the weak force between the layers of transition metal dichalcogenides, for ion intercalation, and the conversion chemistry with lithium-ions. While drawbacks such as capacity degradation, and degradation reaction with electrolytes at low discharge potential still exists, an alternate route can be achieved by incorporating layered transition metal dichalcogenides with the polymer-derived silicon-based ceramic, such as silicon oxycarbide (SiOC). SiOC functionalized MoSe2 electrode curbs disadvantages such as capacity degradation, leading to a composite electrode material possessing long term stable cycling in Li-ion batteries (LIBs). In this study, we report a synthesis process for the freestanding PVP/SiOC/MoSe2 fiber mats via electrospinning and further heat treatment. After characterizing the structure of PVP/SiOC/MoSe2 fiber mats via electron microscopy and spectroscopic techniques (such as SEM, TEM and XPS) the composite electrode was used in LIBs, that showed improved cycling stability which may pave the way to build promising electrodes for LIBs.