The urgency of climate change mitigation calls for a profound shift in personal behavior. This paper investigates psycho-social correlates of extra mitigation behavior in response to climate change, while also testing for potential (unobserved) heterogeneity in European citizens' decision-making. A person's extra mitigation behavior in response to climate change is conceptualized-and differentiated from common mitigation behavior-as some people's broader and greater levels of behavioral engagement (compared to others) across specific self-reported mitigation actions and behavioral domains. Regression analyses highlight the importance of environmental psychographics (i.e., attitudes, motivations, and knowledge about climate change) and socio-demographics (especially country-level variables) in understanding extra mitigation behavior. By looking at the data through the lens of segmentation, significant heterogeneity is uncovered in the associations of attitudes and knowledge about climate change-but not in motivational or socio-demographic links-with extra mitigation behavior in response to climate change, across two groups of environmentally active respondents. The study has implications for promoting more ambitious behavioral responses to climate change, both at the individual level and across countries.