The current study examined the structural and functional connectivity of the cerebro-cerebellar network of verbal working memory as proposed by Chen and Desmond (2005a). Diffusion spectrum imaging was employed to establish structural connectivity between cerebro-cerebellar regions co-activated during a verbal working memory task. The inferior frontal gyrus, inferior parietal lobule, pons, thalamus, superior cerebellum and inferior cerebellum were used as regions of interest to reconstruct and segment the contralateral white matter cerebro-cerebellar circuitry. The segmented pathways were examined further to establish the relationship between structural and effective connectivity as well as the relationship between structural connectivity and verbal working memory performance. No direct relationship between structural and effective connectivity was found but the results demonstrated that structural connectivity is indirectly related to effective connectivity as DCM models that resembled more closely with underlying white matter pathways had a higher degree of model inference confidence. Additionally, it was demonstrated that the structural connectivity of the ponto-cerebellar tract was associated with individual differences in response time for verbal working memory. The findings of the study contribute to further our understanding of the relationship between structural and functional connectivity and the impact of variability in verbal working memory performance.