Penta-graphene is a new 2D allotrope of carbon exclusively consists of pentagons in a planar sheet geometry. In this work, we explored that if it can be a substrate for hydrogen spillover. The density-functional theory (DFT) studies show that the H atom can stably adsorb on sp(2) carbons. The saturation hydrogen storage density of penta-graphene is estimated to be 5.3 wt%. The Pt-4, Pd-4 Ni-4, and Ti-4 clusters are used as the catalyst for hydrogen spillover, and the migration barriers are 1.25, 1.07, 1.03 and 1.35 eV, respectively. The kinetic Monte Carlo simulations are performed to study the migration process for massive H atoms. The results show that the optimal reaction temperatures are 467, 405, 390, and 504 K for Pt-4, Pd-4, Ni-4, and Ti-4 catalyst, respectively. For Pd-4 and Nil catalysts, the spillover reaction can occur at the appropriate temperature (355 and 340 K, respectively) for onboard hydrogen storage systems applied to light-duty vehicles. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.