© 2015 Taylor & Francis. In this paper, we extend the concept of mutual exclusivity proposed by [Dhaene, J. & Denuit, M. (1999). The safest dependence structure among risks. Insurance: Mathematics and Economics25, 11–21] to its tail counterpart and baptize this new dependency structure as tail mutual exclusivity. Probability levels are first specified for each component of the random vector. Under this dependency structure, at most one exceedance over the corresponding Value-at-Risks (VaRs) is possible, the other components being zero in such a case. No condition is imposed when all components stay below the VaRs. Several properties of this new negative dependence concept are derived. We show that this dependence structure gives rise to t...