By means of VDW-DF and M06-2X calculations we studied hydrogen storage on biphenylene nanostructures. The biphenylene sheet adsorbs lithium significantly stronger than graphene and graphyne, since the adsorption energy (AE) is 0.67eV larger. The Li-doped sheet can adsorb 7.4wt.% of H 2 , with an average AE of −0.20eV. When calcium is used as dopant, the AE of H 2 are lower than those computed for Li-doped systems. The Ca-doped sheet poses a triplet ground-state, but the adsorption of 5 H 2 molecules turns the singlet-state lower by 0.47eV. The doped biphenylene nanostructures are interesting materials to study the storage of hydrogen and lithium.