The paper is concerned with determination of the energy spectra of hydrogen in steels by the Vacuum Hot Extraction method (VHE). The investigation is performed on example of 34CrNiMo6 steel and the benchmark study of Vacuum Hot Extraction method and Thermal Desorption Spectroscopy (TDS) is provided. The spectrum of the hydrogen binding energy and the hydrogen concentration in samples are identified. Two additional energy levels are found out which are possibly related to strong covalent bonds. An advantage of VHE in comparison with TDS is that VHE approach does not require pre-saturation of samples by hydrogen. It keeps the original structure of the samples and ensures that all types of traps are not destroyed in tests. Additionally, the present approach opens new opportunity of accurate analysis on the base of the model of hydrogen multichannel diffusion in steels. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.