Given that the common medium in existing green roofs is a single layer composed of organic and inorganic substrates, seven pilot-scale dual-substrate-layer extensive green roofs (G1–G7), which include nutrition and adsorption substrate layers, were constructed in this study. The effectiveness of porous inert substrates (activated charcoal, zeolite, pumice, lava, vermiculite and expanded perlite) used as the adsorption substrate for stormwater retention was investigated. A single-substrate-layer green roof (G8) was built for comparison with G1–G7. Despite the larger total rainfall depth (mm) of six types of simulated rains (43.2, 54.6, 76.2, 87.0, 85.2 and 86.4, respectively), the total percent retention of G1–G7 varied between 14% and 82% with an average of 43%, exhibiting better runoff-retaining capacity than G8 based on the maximum potential rainfall storage depth per unit height of adsorption substrate. Regression analysis showed that there was a logarithmic relationship between cumulative rainfall depth with non-zero runoff and stormwater retention for G1–G4 and a linear relationship for G5–G8. To enhance the water retention capacity and extend the service life of dual-substrate-layer extensive green roofs, the mixture of activated charcoal and/or pumice with expanded perlite and/or vermiculite is more suitable as the adsorption substrate than the mixture containing lava and/or zeolite.