Nonstoichiometric SiO x is a kind of very attractive anode material for high-energy lithium-ion batteries because of a high specific capacity and facile synthesis. However, the poor electrical conductivity and unstable electrode structure of SiO x severely limit its electrochemical performance as anode in lithium-ion batteries. In this work, highly durable sugar apple-shaped SiOx@C nanocomposite spheres are fabricated to achieve significantly improved electrochemical performance. The composite is synthesized by homogenous one-pot synthesis, using ethyltriethoxysilanes (EtSi(OEt)3) and resorcinol/formaldehyde (RF) as starting materials. The morphology, composition and structure of the composite are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), elemental analysis (EA) and X-ray photoelectron spectroscopy (XPS). At a current density of 50 mA g−1, the sugar apple-shaped SiOx@C spheres exhibit a stable discharge capacity of about 630 mAh g−1 calculated on the total mass of both SiOx and C. At a current density of 100 mA g−1, a stable discharge capacity of about 550 mAh g−1 is obtained and the capacity has been kept up to 400 cycles. The excellent cycling performance is attributed to the homogeneous dispersion of SiOx in disordered carbon at the nanometer scale and the unique structure of the composite.