Several studies have shown that body satisfaction affects interpersonal functioning. However, few have studied the specific interpersonal correlates of another important body image dimension, appearance investment—that is, the importance a woman places on appearance. We used an experience sampling design with PDA (personal digital assistant) devices to assess how 92 college women's appearance investment is related to perceptions of everyday social interactions and to investigate the association of these perceptions with mood and self-esteem. For 1 week, participants completed electronic diaries of their mood, self-esteem, and perceptions of one-on-one interactions. High appearance investment was associated with a stronger relationship between perceived communion of the interaction and negative mood and self-esteem. Notably, highly appearance-invested women did not report differences in average momentary levels of perceived communion or agency in interactions, negative mood, or self-esteem when compared to women with lower appearance investment. In contrast, women with low body satisfaction reported lower average perceptions of communion and self-esteem as well as higher average negative mood compared to women with higher body satisfaction, but no relationships among perceptions and self-esteem and mood were found. Thus, self-esteem and negative mood in women high in appearance investment might be contingent on perceptions of communion in interactions, even though they appear to have average levels of mood and self-esteem in general. This mood and self-esteem contingency could predispose appearance-invested women to psychological distress or eating pathology.