Molecular dynamics (Born–Oppenheimer) simulations based on density functional theory have been carried out to investigate the solvation structure of monovalent Na+ and K+ cations in water under ambient conditions. Four recently proposed van der Waals (vdW) density functionals (LMKLL, DRSLL, DRSLL-PBE, DRSLL-optB88), the semiempirical vdW method of Grimme (BLYP-D3) and conventional gradient-corrected (GGA-BLYP) density functionals are applied in order to evaluate their accuracy in describing the hydration structure of alkali metal ions. Theoretical results are compared to available experimental data. Our results indicate that addition of corrections accounting for dispersion forces significantly improves the agreement between predicted and measured coordination numbers for both Na+ and K+ cations. Analysis of radial distribution functions brings further support to the notion that the choice of the generalised gradient approximation density functional impacts crucially on the computed structural properties. DRSLL-optB88 and BLYP-D3 provide the best agreement with experiment.