A B- and N-doped microporous carbon has been synthesized via a substitution reaction. The obtained carbon exhibited much higher surface area than the previously reported B- and N-doped carbon. The hydrogen storage measurements indicated that the B- and N-doped microporous carbon had a 53% higher storage capacity than the carbon materials with similar surface areas. Furthermore. hydrogen storage via spillover was studied on Ru-supported B- and N-doped microporous carbon and a storage capacity of 1.2 wt % at 298 K and 10 MPa was obtained, showing an enhancement factor of 2.2. Ab initio molecular orbital calculations were also perfomed for the binding energies between the spiltover hydrogen atom and various sites on the doped carbon. The theoretical calculations can explain the experitmental results well, which also shed light on the most favorable and possible sites with which the spiltover hydrogen atoms bind. (C) 2009 American Institute of Chemical Engineers AIChE J, 55: 1823-1833, 2009