Microstructure influence on hydrogen trapping in a Cr-Mo type steels −2.25Cr 1Mo and 2.25Cr 1Mo 0.25V− was studied by means of electrochemical permeation test, thermal desorption spectrometry, scanning and transmission electron microscopy analysis. Both steels, used in hydrogenation reactors, in as received and artificial aged conditions exhibit a bainitic microstructure with CrxMoy and CrxMoyVz carbides finely dispersed. The hydrogen diffusivity for the 2.25Cr-1Mo-0.25V is lower than 2.25Cr-1Mo due to its higher carbide precipitation. At aged conditions TDS on samples cathodically charged with hydrogen showed an increase on the hydrogen trapping capacity for 2.25Cr-1Mo and a reduction for the vanadium modified steel, compared with the as-received state.