Across three studies, we examined non-Black children's spontaneous associations with targets who differed by both race and emotional expression. Children aged 5 to 10 years (N = 419; 215 girls; 58% White; 65% of household incomes >$75,000/year) completed Implicit Association Tests (IAT; Greenwald et al., 2003) containing smiling Black and neutral White target faces. In all three studies, when children categorized these faces by emotional expression, they showed relatively more positive associations with smiling Black targets over neutral White targets, as compared with when they categorized these faces by race. This was the case when children were shown how to categorize these faces (Studies 1 and 2) and when they spontaneously categorized by race or emotional expression on an Ambiguous-Categorization IAT that allowed for categorization by race and/or emotion (Studies 2 and 3). In Study 3, after watching an adult explain that she was categorizing racially diverse faces by emotional expression in a seemingly unrelated card-sorting task, children were also relatively faster to pair smiling Black faces with pleasant images and neutral White faces with unpleasant images on this Ambiguous-Categorization IAT compared with children in a control condition. Older children were more likely to spontaneously categorize primarily by race (Studies 2 and 3) but were also more likely to categorize by emotion following the intervention (Study 3) compared with younger children. Together, these studies provide insight into children's social categorization processes and spontaneous associations with targets who differ systematically across multiple perceptually salient categories.