Green roofs (GRs) have been one of the most popular solutions for water harvesting in urban areas. Apart from their water retention role and increasing biodiversity, they constitute the missing link between the built and the natural environment, which is required for sustainable human living in cities. This paper aims to calculate the ecological (EE) and economic effect (EcE) of water harvesting via GRs, by contrasting with a traditional roof, and to perform an economic analysis of the social cost benefits that GRs generate during their life cycle, using the Net Present Value (NPV) method. All the calculations and analyses were conducted for both intensive and extensive GRs in 11 of the largest municipalities in Poland, with a population of >250,000 inhabitants. According to the results of this study, water retention and the economic and ecological effects of GRs are highest in the municipalities with the highest assumed number of GRs (Warsaw, Krakow, Wroclaw, and Szczecin). The average EE and EcE equals 507,000 m3/yr and 621,000 USD/yr. The NPV results show that the effectiveness of investments in intensive GRs is, to a certain extent, more significant than in extensive GRs and the average equals 60.77 and 4.47 USD/yr for intensive and extensive GRs, respectively. The results could serve as a reference for the evaluation and optimization of the energy efficiency of rainwater harvesting schemes, in European cities.