Violent extremism is often explicitly motivated by commitment to abstract ideals such as the nation or divine law—so-called “sacred” values that are relatively insensitive to material incentives and define our primary reference groups. Moreover, extreme pro-group behavior seems to intensify after social exclusion. This fMRI study explores underlying neural and behavioral relationships between sacred values, violent extremism, and social exclusion. Ethnographic fieldwork and psychological surveys were carried out among 535 young men from a European Muslim community in neighborhoods in and around Barcelona, Spain. Candidates for an fMRI experiment were selected from those who expressed willingness to engage in or facilitate, violence associated with jihadist causes; 38 of whom agreed to be scanned. In the scanner, participants were assessed for their willingness to fight and die for in-group sacred values before and after an experimental manipulation using Cyberball, a toss ball game known to yield strong feelings of social exclusion. Results indicate that neural activity associated with sacred value processing in a sample vulnerable to recruitment into violent extremism shows marked activity in the left inferior frontal gyrus, a region previously associated with sacred values and rule retrieval. Participants also behaviorally expressed greater willingness to fight and die for sacred versus nonsacred values, consistent with previous studies of combatants and noncombatants. The social exclusion manipulation specifically affected nonsacred values, increasing their similarities with sacred values in terms of heightened left inferior frontal activity and greater expressed willingness to fight and die. These findings suggest that sacralization of values interacts with willingness to engage in extreme behavior in populations vulnerable to radicalization. In addition, social exclusion may be a relevant factor motivating violent extremism and consolidation of sacred values. If so, counteracting social exclusion and sacralization of values should figure into policies to prevent radicalization.