[Ni-2(btc)(en)(2)](n) coordination polymer exhibits a layered two-dimensional structure with weak interaction between the layers. Correlation of experimental measurements, DFT calculations and molecular simulations demonstrated that its structural features, primarily the inherent flexibility of the layered polymeric structure, lead to improved hydrogen storage performance at room temperature, due to significant enhancement in isosteric heats of hydrogen adsorption. Volumetric measurements of hydrogen adsorption at room temperature show up to 0.3 wt.% hydrogen absorbed at 303 K and 2.63 bar of hydrogen pressure, with isosteric heats of adsorption of about 12.5 kJ mol(-1). Predicted performance at room temperature is 1.8 wt.% at 48 bar and 3.5 wt.% at 100 bar, better than both MOF-5 and NU-100, with calculated values of isosteric heats for adsorption of hydrogen in 8-13 kJ mol(-1) range at both 77 K and 303 K. Grand canonical Monte Carlo calculations show that this material, at 77 K, exhibits gravimetric hydrogen densities of more than 10 wt.% (up to 8.3 wt.% excess) with the corresponding volumetric density of at least 66 gL(-1), which is comparable to MOF-5, but achieved with considerably smaller surface area of about 2500 m(2) g(-1). This study shows that layered two-dimensional MOFs could be a step towards MOF systems with significantly higher isosteric heats of adsorption, which could provide better room temperature hydrogen storage capabilities. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.