Human learning is a complex phenomenon that varies greatly among individuals and is related to the microstructure of major white matter tracts in several learning domains, yet the impact of the existing myelination of major white matter tracts on future learning outcomes remains unclear. We employed a machine-learning model selection framework to evaluate whether existing microstructure might predict individual differences in the potential for learning a sensorimotor task, and further, if the mapping between the microstructure of major white matter tracts and learning was selective for learning outcomes. We used diffusion tractography to measure the mean fractional anisotropy (FA) of major white matter tracts in 60 adult participants who then underwent training and subsequent testing to evaluate learning. During training, participants practiced drawing a set of 40 novel symbols repeatedly using a digital writing tablet. For testing, we measured drawing learning as the slope of draw duration over the practice session; we measured visual recognition learning as the performance accuracy in an old/new 2-AFC recognition task. We performed two separate analyses, one that assessed the relationship between pre-training FA and learning to draw novel symbols and a second that assessed the relationship between pre-training FA and learning to visually recognize symbols after training. Both analyses focused on the microstructure of white matter tracts that connect dorsal and ventral cortices, the posterior vertical pathway (PVP), as well as tracts within the dorsal motor system and within the ventral perceptual system. Results demonstrated that the microstructure of major white matter tracts selectively predicted learning outcomes, with left hemisphere pArc and SLF 3 tracts predicting drawing learning and the left hemisphere MDLFspl predicting visual recognition learning. These results were replicated in a repeat, held-out data set and supported with complementary analyses. Overall, results suggest that individual differences in the microstructure of human white matter tracts may be selectively related to future learning outcomes that arise from a single experience and open avenues of inquiry concerning the impact of existing tract myelination and individual differences in the potential for learning.