The near-edge X-ray absorption fine structure at the carbon K edge was measured for determining the chemical state of interstitial carbon in a low-carbon steel. In addition, the wavelength dependence of the photoelectron spectrum of the surface of the steel was evaluated, and a contamination and oxidation layer of 3 nm thickness was found. As a result, it was possible to observe a change in the chemical state of carbon existing in bulk iron located deeper than the oxidation and contamination layers, by evaluating the difference spectra between the sample and a reference. Furthermore, by evaluating the shape change of the difference spectra based on the heat treatment time, it was found that the chemical state of carbon in bulk iron changes with heat treatment.