In recent decades, the majority of cities in developing countries have grown rapidly and have experienced increasing environmental problems. These changes have generated a broad discussion on urban sustainability and development. In this discussion, it is fundamental to establish methods for measuring urban sustainability using a quantitative approach. This research seeks to estimate and evaluate the environmental, social, and economic efficiency of cities in a developing country, Colombia, using data envelopment analysis to determine the changes that occurred between 2005 and 2013. In this study, indicators related to economic, environmental, and social performance are used with the objective of analyzing efficiency from urban sustainability. The results indicate differences among cities, where the efficient cities show adequate resource use, lower environmental impacts, improved social conditions, and guaranteed economic growth and development. Moreover, as the city scale increases, urban sustainability declines. All these findings are important in the formulation and design of adequate urban policies to improve and strengthen sustainability and social welfare over the long term, particularly in cities in developing countries.