The influence of moisture content on substrate thermal conductivity at different temperatures was investigated for four different commercially available substrates for green roofs. In the unfrozen state, as moisture content increased, thermal conductivity increased linearly. In the phase transition zone between +5 and −10 °C, as temperature decreased, thermal conductivity increased sharply during the transition from water to ice. When the substrate was frozen, thermal conductivity varied exponentially with substrate moisture content prior to freezing. Power functions were found between thermal conductivity and temperature. Two equally sized, green roof test cells were constructed and tested to compare various roof configurations including a bare roof, varying media thickness for a green roof, and vegetation. The results show that compared with the bare roof, there is a 75% reduction in the interior temperature’s amplitude for the green roof with 150 mm thick substrate. When a sedum mat was added, there was a 20% reduction in the amplitude of the inner temperature as compared with the cell without a sedum mat.