A converging literature has revealed the existence of a set of largely consistent, hierarchically organized personality traits, that is broader traits are able to be differentiated into more fine-grained traits, in both humans and chimpanzees. Despite recent work suggesting a neural basis to personality in chimpanzees, little is known with regard to the involvement of limbic structures (i.e., amygdala and hippocampus), which are thought to play important roles in emotion. Using saved maximum likelihood estimated exploratory factor scores (two to five factors) in the context of a series of path analyses, the current study examined associations among personality dimensions across various levels of the personality hierarchy and individual variability of amygdala and hippocampal grey matter (GM) volume in a sample of captive chimpanzees (N=191). Whereas results revealed no association between personality dimensions and amygdala volume, a more nuanced series of associations emerged between hippocampal GM volume and personality dimensions at various levels of the hierarchy. Hippocampal GM volume associated most notably with Alpha (a dimension reflecting a tendency to behave in an undercontrolled and agonistic way) at the most basic two-factor level of the hierarchy; associated positively with Disinhibition at the next level of the hierarchy (“Big Three”); and finally, associated positively with Impulsivity at the most fine-grained level (“five-factor model”) of the hierarchy. Findings underscore the importance of the hippocampus in the neurobiological foundation of personality, with support for its regulatory role of emotion. Further, results suggest the importance of the distinction between structure and function, particularly with regard to the amygdala.