Executive functioning in preschool children is important for building social relationships during the early stages of development. We investigated the brain dynamics of preschool children during an attention-shifting task involving congruent and incongruent gaze directions in emotional facial expressions (neutral, angry, and happy faces). Ignoring distracting stimuli (gaze direction and expression), participants (17 preschool children and 17 young adults) were required to detect and memorize the location (left or right) of a target symbol as a simple working memory task (i.e., no general priming paradigm in which a target appears after a cue stimulus). For the preschool children, the frontal late positive response and the central and parietal P3 responses increased for angry faces. In addition, a parietal midline α (Pmα) power to change attention levels decreased mainly during the encoding of a target for angry faces, possibly causing an association of no congruency effect on reaction times (i.e., no faster response in the congruent than incongruent gaze condition). For the adults, parietal P3 response and frontal midline θ (Fmθ) power increased mainly during the encoding period for incongruent gaze shifts in happy faces. The Pmα power for happy faces decreased for incongruent gaze during the encoding period and increased for congruent gaze during the first retention period. These results suggest that adults can quickly shift attention to a target in happy faces, sufficiently allocating attentional resources to ignore incongruent gazes and detect a target, which can attenuate a congruency effect on reaction times. By contrast, possibly because of underdeveloped brain activity, preschool children did not show the happy face superiority effect and they may be more responsive to angry faces. These observations imply a crucial key point to build better relationships between developing preschoolers and their parents and educators, incorporating nonverbal communication into social and emotional learning.