Urban watercourses are vital natural elements within cities that can provide multiple ecosystem services to society. However, rivers are under continuous urbanization pressures in developing urban areas like the post-socialist countries. We focus on the Western Balkans (WB) countries to assess the relationship between the urban rivers and the respective metropolitan capital areas. First, we analyze the land use and land cover (LULC) along the respective watercourse at five buffer distances. Our work relies on Urban Atlas data acquired from the European Environment Agency. According to our results the natural land surfaces share on the waterfronts range between 89% along Lana River (Tirana) and 22% along Miljacka River (Sarajevo). The green surfaces share along the Moraca River (Podgorica) and Vardar River (Skopje) are more constant along five buffer distances. We report the results of each case in detail and compare among the selected five developing European urban centres with respect to their unique socio-political background. Our findings highlight the importance of natural and semi-natural surfaces presence along the urban rivers in support of sustainable decision-making at multiple spatial and jurisdiction levels in the WB, which is a hotspot of political, economic, and urban transformation triggered by EU membership aspirations.