The study of environmental concern has repeatedly shown the need to investigate environmentally significant behaviours. Beliefs about ecological behaviours (and the frequency with which they are performed) have become a more precise indicator of the environmental concern. This study examined the differences between residents in rural and urban zones. To do this, an expressed ecological behaviour scale (EEBS) was designed. The instrument included 24 items about pro-environmental behaviours in daily life. It was administered to a sample of 840 participants, 400 from rural places and 440 from Madrid. Across the whole sample, the three behaviours engaged in most often were: taking care of natural protected areas, extinguishing unnecessary lights, and turning off the faucet while brushing teeth. The three behaviours performed least often were: collaborating with environmentalist organizations focused on biodiversity, installing flow constrictors in water faucets, and recycling oil. Some significant urban-rural differences were found. Urban residents report paying attention more often than rural residents to energy efficiency labels when buying domestic appliances, and they use public transport more often. Rural residents separate their garbage more often, recycle packaging more often, and recycle oil more often than urban residents. In sum, these results show that a different profile exists in the ecological orientation of urban and rural residents. Urban residents seem to define ecological questions more in terms of the cost of energy, whereas rural residents seem to focus their environmental concern more on pollution. Thus, socio-structural factors (as in this study, place of residence) partly define residents’ approach to acting on their ecological concern.