Silicon-containing polyester from tetramethoxysilane, ethylene glycol, and o-Phthalic anhydride were used as encapsulating materials for silicon nano powders (SiNP) via electrospinning, with Polyacrylonitrile (PAN) as spinning additives. In the correct quantities, SiNP could be well encapsulated in nano fibers (200–400 nm) using scanning electron microscopy (SEM). The encapsulating materials were then carbonized to a Si-O-C material at 755 °C (Si@C-SiNF-5 and Si@C-SiNF-10, with different SiNP content). Fiber structure and SiNP crystalline structure were reserved even after high-temperature treatment, as SEM and X-ray diffraction (XRD) verified. When used as lithium ion battery (LIB) anode materials, the cycling stability of SiNPs increased after encapsulation. The capacity of SiNPs decreased to ~10 mAh/g within 30 cycles, while those from Si@C-SiNF-5 and Si@C-SiNF-10 remained over 500 mAh/g at the 30th cycle. We also found that adequate SiNP content is necessary for good encapsulation and better cycling stability. In the anode from Si@C-SiNF-10 in which SiNPs were not well encapsulated, fibers were broken and pulverized as SEM confirmed; thus, its cycling stability is poorer than that from Si@C-SiNF-5.