The melamine foam presents a unique microstructure characterized by an interconnected network of solid struts, which form the edges and faces of high porosity open cells. This study investigates the influence of pore size distribution on acoustic properties for three commercially available melamine foams. Based on the measured transport parameters, a top-down approach is employed to determine the equivalent Kelvin-cell size corresponding to each transport parameter. The differences found in these equivalent pore sizes indicate that the mono-size model is not suitable for these materials, a difference from which a quantitative estimate of the level of polydispersity can be deduced (using macro-scale information). The polydispersity was confirmed from experimental evidence at micro-scale from the analysis of SEM images. Moreover, the measurements collected at micro-scale (average pore size and its standard deviation) can be used as input data to determine the transport and sound absorbing behavior of melamine foam samples from structure-property relationships available for open cell microstructures. This work provides evidence that the polydispersity of melamine foams should be taken into account to obtain an accurate and consistent picture of microstructure and transport properties of such open cell high porosity foams.