Humans differ substantially in their ability to imagine spatial transformations of novel stimuli (i.e., mental rotation). Whereas "high-spatial" individuals are able to maintain high-quality representations even after complex mental transformations, "low-spatial" individuals often experience substantial degradation of the initial representation. Even though subdivisions of the posterior parietal cortex are known to instantiate the necessary spatial transformations, a direct demonstration of neuroanatomical differences predicting this behavioral variability is currently missing. Because recent evidence suggests that interindividual differences on the behavioral level might be related to regionally specific white matter organization, we addressed this question using diffusion tensor imaging in combination with well-established psychometric tests. As expected, behavioral results revealed a substantial disparity in mental rotation performance. Most importantly, despite controlling for differences in spatial short-term memory capacity, we observed a tight relationship between mental rotation proficiency and white matter organization near the anterior part of the intraparietal sulcus. Whereas high-level proficiency was paralleled by high fractional anisotropy (FA) values, the opposite pattern was observed in "low spatials". The present results strongly indicate that the efficiency of information transfer between posterior parietal regions involved in the mental transformation process could be one decisive factor in individual spatial visualization proficiency.