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Current knowledge of the white matter changes in large-scale brain networks in adult attention deficit hyperactivity disorder (ADHD) is scarce. We collected diffusion-weighted magnetic resonance imaging data in 40 adults with ADHD and 36 neurotypical controls and used constrained spherical deconvolution based tractography to reconstruct whole-brain structural connectivity networks. We used network-based statistics (NBS) and graph theoretical analysis to investigate differences in these networks between the adults with ADHD and neurotypical controls. We also tested whether structural connectivity was related to ADHD symptoms or performance in a continuous performance test (CPT). NBS revealed two unilateral networks in which structural connectivity was decreased in the participants with ADHD compared to the neurotypical controls. These large-scale networks encompassed subcortical and corticocortical frontal, temporal, parietal and occipital structures, including parts of dorsal and ventral attention networks and visual and somatomotor systems. Graph theoretical analysis did not reveal global or local differences between the ADHD and control groups. We found no associations between structural connectivity and ADHD symptoms or CPT performance. In conclusion, our results suggest that abnormal structural wiring of the brain in adult ADHD is manifested as widespread intrahemispheric hypoconnectivity in brain networks previously associated with ADHD in functional neuroimaging studies.