This work deals with the investigations of hydrogen adsorption energies of the Li functionalized Covalent Organic Framework-366 (COF-366) by using the density functional theory method. Based on total energy calculations, it was found that Li atom is preferentially trapped at the center site of the tetra(p-amino-phenyl) porphyrin and the onN site of a terephthaldehyde chain. Moreover, hydrogen adsorption energies per H-2 for 1-3 H-2 loadings range from 0.03 to 0.22 eV. According to ab initio molecular dynamics simulations, our results found that hydrogen capacities of Li functionalized COF-366 at ambient pressure are 2.06, 1.58, and 1.05 wt% for 77, 150 and 298 K, respectively. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.