The global society is overwhelmed by growing social inequality and environmental pollution. Especially, the fashion industry has been linked to hazardous clothing wastes and exploitation of labor in poor countries. We acknowledge that the sustainability philosophy could be an alternative governing principle that can lead us to a better future for the fashion industry. This study investigates brain responses of fashion professionals and consumers as they are presented with sustainable fashion of luxury and SPA brands. Using functional magnetic resonance imaging (fMRI), the whole brain responses of participants were measured and analyzed to reveal how their brain responses differ depending on fashion products’ brand type and certification mark. We build an online education platform for professionals and lay consumers on the subject of sustainable fashion. Brain responses are measured from both groups of professionals and consumers while they are exposed to sustainable fashion products of luxury and SPA brands. A group of subjects watch the online educational program while under the counterpart condition subjects see another video of the same length, unrelated to sustainability. BOLD measures are acquired using Siemens 3T scanner and analyzed using SPM 12 software. We find selective brain activation patterns that can distinguish the educated group from the uneducated ones. The practical implication of this study is that we must do our best to build a sustainability education program which can motivate professionals and consumers effectively, by stimulating both cognitive and affective bases of behavioral change.