Attention-deficit/hyperactivity disorder has been identified to involve impairment of large-scale functional networks within gray matter, and recent studies have suggested that white matter, which also encodes neural activity, can manifest intrinsic functional organization similar to that of gray matter. However, the alterations of white matter functional networks in attention-deficit/hyperactivity disorder remain unknown. We recruited a total of ninety-nine children, including sixty-six drug-naïve patients and thirty-three typically developing controls aged from six to fourteen, to characterize the alterations of functional networks within white matter in drug-naïve children with attention-deficit/hyperactivity disorder. Using clustering analysis, resting-state functional MRI data in the white matter were parsed into different networks. Intrinsic activity within each network and connectivity between networks as well as the associations between network activity strength and clinical symptoms were assessed. We identified eight distinct white matter functional networks: the default mode network, the somatomotor network, the dorsal attention network, the ventral attention network, the visual network, the deep frontoparietal network, the deep frontal network, and the inferior corticospinal-posterior cerebellum network. The default mode, somatomotor, dorsal attention and ventral attention networks showed lower spontaneous neural activity in patients. In particular, the default mode network and the somatomotor network largely showed higher connectivity with other networks, which correlated with more severe hyperactive behavior, while the dorsal and ventral attention networks mainly had lower connectivity with other networks, which correlated with poor attention performance. In conclusion, there are two distinct patterns of white matter functional networks in children with attention deficit/hyperactivity disorder, with one being the hyperactivity related hot networks including default mode network and somatomotor network and the other being inattention related cold networks including dorsal attention and ventral attention network. These results extended upon our understanding of brain functional networks in attention-deficit/hyperactivity disorder from the perspective of white matter dysfunction.