Green roofs can be a valid solution for stormwater management in urban environments. The objective of this study was to develop a laboratory procedure for the hydraulic characterization of artificial substrates, used in the realization of green roofs, based on transient evaporation and steady-state unit hydraulic gradient (UHG) experiments. The retention, θ(h), and hydraulic conductivity, K(h), curves of two commercial substrates Terra Mediterranea® (TMT) and AgriTERRAM® (ATV) and a specifically developed substrate made by mixing peat, compost and sandy loam soil (MIX) were investigated. The unimodal van Genuchten–Mualem (VGM) hydraulic functions obtained by the direct evaporation method with different choices of the fitting parameters were compared with UHG measurements of K(h) conducted close to saturation. A numerical inversion of the transient evaporation experiments performed by Hydrus-1D software was also conducted, assuming that the hydraulic properties could be expressed either by unimodal or bimodal VGM models. The results indicated that an appropriate a priori choice of the residual water content parameter improved the estimation of the water retention curve. Moreover, the water retention data estimated from the direct evaporation method were not statistically different from those obtained with the inverse Hydrus-1D. The unsaturated hydraulic conductivity estimations obtained by the direct and inverse methods were highly correlated and the use of the bimodal VGM model improved the estimation of K(h) in the wet range. The numerical inversion of laboratory evaporation data with the hydraulic characteristics expressed by the bimodal VGM model proved to be a reliable and effective procedure for hydraulic characterization of artificial substrates, thus improving the reliability of simulated water fluxes in green roofs.