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Word learning plays a central role in language development and is a key predictor for later academic success. The underlying neural basis of successful word learning in children is still unknown. Here, we took advantage of the opportunity afforded by diffusion-weighted magnetic resonance imaging to investigate neural plasticity in the white matter of typically developing preschool children as they learn words. We demonstrate that after 3 weeks of word learning, children showed significantly larger increases of fractional anisotropy (FA)