A novel anode material for lithium-ion batteries, graphene-wrapped Si nanoparticles (NPs) embedded in carbon composite nanofibers (CCNFs) with G/Si, is fabricated by electrospinning and subsequent thermal treatment. In CCNFs with G/Si, Si NPs are distributed and preserved inside the CNF surface because the graphene wrapping the Si NPs help prevent agglomeration and ensure a good dispersion of Si NPs inside the CNF matrix. 20-GSP prepared from a weight ratio of 20 wt% of G/Si to polyacrylonitrile exhibits stable capacity retention and a reversible capacity of above 600 mAh g−1 up to 100 cycles. The high cycling performance and superior reversible capacity of the 20-GSP anode can be attributed to the one-dimensional nanofibrous structure with non-agglomerated Si NPs in the CNF matrix, which promotes charge transfer, maintains a stable electrical contact, and buffers the Si volume expansion.