The nature of the chemical bonding in an amorphous Si-coated carbon nanotube (Si-CNT) anode, and its evolution upon electrochemical cycling, have been investigated using comprehensive X-ray absorption spectroscopy (XANES) at the Si L- and K-edges, along with the C and O K-edges. The Si nanolayer on the CNT is found to be anchored to the CNT via Si–O–C bonding. This bond weakens upon electrochemical cycling, accompanied by the generation of Li₂CO₃ on the surface of the Si-CNT. These findings are crucial in designing further improved Si–C composite anodes for lithium ion batteries.