Binder- and conducting additive-free Si-O-C composite layers are deposited electrochemically under potentiostatic conditions from sulfolane-based organic electrolyte. Quartz crystal microbalance with damping monitoring is used for evaluation of the layer growth and its physical properties. The sodiation-desodiation performance of the material is afterward explored in Na-ion electrolyte. In terms of specific capacity, rate capability, and long-term electrochemical stability, the experiments confirm the advantages of applying the electrochemically formed Si-O-C structure as anode for Na-ion batteries. The material displays high (722 mAh g^-1) initial reversible capacity at j = 70 mA g^-1 and preserves stable long-term capacity of 540 mAh g^-1 for at least 400 galvanostatic cycles, measured at j = 150 mA g^-1. The observed high performance can be attributed to its improved mechanical stability and accelerated Na-ion transport in the porous anode structure. The origin of the material electroactivity is revealed based on X-Ray photoelectron spectroscopic analysis of pristine (as deposited), sodiated, and desodiated Si-O-C layers. The evaluation of the spectroscopic data indicates reversible activity of the material due to the complex contribution of carbon and silicon redox centers.