The combination of electrospinning and electrospray processes has been used to fabricate three different hierarchical network architectures based on nanoscale Si and Polyacrylonitrile (PAN). Among these hierarchical architectures, the core-shell Si/PAN structure and the Si/PAN multilayer structure have significantly improved the cycling performance with high capacity and good capacity retention. Cyclization has also been performed to form the hierarchical conductive framework, which provides a continuous electron transport network and high porosity to address the volume expansion during electrochemical reactions. By integrating electrospray process in the synthesis process, a greatly improved capacity is achieved with a high reversible area capacity over 2mAh/cm2. This work will present the results of our systematic investigation on structure-property relationships in the Si/PAN hierarchical architectures.