The manufacturing of novel melamine-formaldehyde rigid foam material, by blowing the melamine-formaldehyde (MF) resin emulsion with pentane and further catalytic and thermal curing, is presented in this work. The process of foaming is described in terms of particular process parameters, which are; the proportions of blowing, curing, emulsifying agents. The examination of the foam, by SEM images, shows that the foam pore sizes are in the range from 150 to 250 µm. The thermal characterization of the obtained foams, is described in terms of thermal conductivity contributions of solid, gas and radiation conduction to total thermal conductivity at atmospheric and vacuum condition. The foam with densities from 50 to 80 kg/m3 achieve thermal conductivity at an atmospheric pressure of 33–34 mW/(m × K), while in a vacuum of 6–7 mW/(m × K). Compared to other organic polymer foams, MF foams have superior fire resistance and chemical stability. The innovation of MF rigid foams presented here, compared to other well-known MF flexible foam, is in their rigid structure, combined with low density and thermal conductivity, which makes this particular foam potentially useful in the manufacture of vacuum insulation panels (VIP).