This study addresses the influence of pore size variation on the effective thermal conductivity of open-cell foam structures. Numerical design procedure which renders it possible to control chosen structural parameters has been developed based on characterization of commercially available open-cell copper foams. Open-porous materials with various pore size distribution were numerically designed using the Laguerre–Voronoi Tessellations procedure. Heat transfer through an isolated structure was simulated with the finite element method. The results reveal that thermal conductivity is strongly related to porosity, which is in agreement with the literature. The influence of pore size distribution has also been observed and compared with analytical formulas proposed in the literature.