Extensive green roofs are urban construction systems that provide thermal regulation and sound proofing for the buildings involved, in addition to providing an urban heat island mitigation or water retention. On the other hand, policies towards reduction of energy consumption, a circular economy and sustainability are core in the European Union. Motivated by this, an experimental study was carried out to evaluate the environmental risk assessment according to release levels of polluting elements on leachates of different green roof substrate mixtures based on recycled aggregates from construction and demolition waste through (i) the performance in laboratory of two procedures: compliance and percolation tests and (ii) an upscaled experimental leaching test for long-term on-site prediction. Four plots were built on a building roof and covered with autochthonous Mediterranean plants in Córdoba, South of Spain. As growing substrate, four mixtures were used of a commercial growing substrate with different proportions of a fine mixed recycled aggregate ranging from 0 to 75% by volume. The results show that these mixtures were classified as non-hazardous materials according to legal limits of the Landfill Directive 2003/33/CE. The release levels registered in extensive green roofs were lower compared to the laboratory test data. This shows how laboratory conditions can overestimate the potential pollutant effect of these materials compared to actual conditions.