The ability to learn new motor skills is crucial for activities of daily living, especially in older adults. Previous work in younger adults has indicated fast and slow stages for motor learning that were associated with changes in functional interactions within and between brain hemispheres. However, the impact of the structural scaffolds of these functional interactions on different stages of motor learning remains elusive. Using diffusion-weighted imaging and probabilistic constrained spherical deconvolution-based tractography, we reconstructed transcallosal white matter pathways between the left and right primary motor cortices (M1-M1), left dorsal premotor cortex and right primary motor cortex (LPMd-RM1) and right dorsal premotor cortex and left primary motor cortex (RPMd-LM1) in younger and older adults trained in a set of bimanual coordination tasks. We used fractional anisotropy (FA) to assess microstructural organisation of the reconstructed white matter pathways. Older adults showed lower behavioural performance than younger adults and improved their performance more in the fast but less in the slow stage of learning. Linear mixed models predicted that individuals with higher FA of M1-M1 pathways improve more in the fast but less in the slow stage of bimanual learning. Individuals with higher FA of RPMd-LM1 improve more in the slow but less in the fast stage of bimanual learning. These predictions did not differ significantly between younger and older adults suggesting that, in both younger and older adults, the M1-M1 and RPMd-LM1 pathways are important for the fast and slow stage of bimanual learning, respectively.