2LiH + MgB2 composite doped with TiO2 (Li-RHC-Ti) is employed with a two-fold purpose: hydrogen purification under a H-2-CO (0.1 mol%) mixture and CO methanation. Upon dynamic cycling under CO-H-2 mixture, hydrogen release curves display a quite stable amount of pure hydrogen of about 10 wt%, short release times of around 60 min, and minor degradation. Gas analysis by Fourier transform infrared spectroscopy (FTIR) after a thermal dehydrogenation process of MgH2 and LiBH4 under CO evidence the conversion of CO to CH4. Li-RHC-Ti dehydrogenated under CO shows the simultaneous formation of CH4, CH3OH, and B(CH3)(3) in the gas phase. X-ray powder diffraction (XRPD) and FTIR characterizations of the solid phases of Li-RHC-Ti after both H-2-CO mixture and CO interactions demonstrate the formation of MgO, LiBO2, and HCOO- species. Li-RHC-Ti acts as a hydrogen source and promoter for the CO conversion. Reaction pathways are proposed based on experimental results and equilibrium composition calculations. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.