Green roofs have the potential to address several of the environmental problems associated with urbanisation, and can be used as mitigation for habitats lost at ground level. Brown roofs (a type of green roof) can be used to mitigate for the loss of brownfield habitat, but the best way of designing these habitats remains unclear. This paper reports an experiment to test the effects of different types of recycled aggregate on the development of vegetation assemblages on brown roof mesocosms. Five recycled aggregates were tested: (1) crushed brick, (2) crushed demolition aggregate, (3) solid municipal waste incinerator bottom ash aggregate, (4) a 1:1 mix of 1 and 2, and (5) a 1:1 mix of 3 and 2. Each was seeded with a wildflower mix that also included some Sedum acre and vegetation development was studied over a six-year period. Species richness, assemblage character, number of plants able to seed, and plant biomass were measured. Drought disturbance was the key factor controlling changes in plant assemblage, but effects varied with substrate treatment. All treatments supported a similar plant biomass, but treatments with a high proportion of crushed brick in the growth substrate supported richer assemblages, with more species able to seed, and a smaller amount of Sedum acre. Crushed brick, or recycled aggregates with a high proportion of crushed brick, are recommended as good growth substrate materials for encouraging brown roof plant diversity. This investigation demonstrates the importance of multi-year studies of green roof development for the generation of robust findings.