Social media appearance preoccupation, which is measured by appearance comparisons, online self-presentation, and appearance-related activity on social media, is a timely construct to understand given the range of psychosocial outcomes tied to social media use. An integration of theories of self-conscious emotions, self-presentation, and social media was used to inform this study exploring appearance shame and envy as correlates of social media appearance preoccupation. Participants (n = 298; 65% women, M-age +/- SD = 23.6 +/- 3.6 years) completed an online self-report survey. Descriptive statistics and structural equation modeling were used to analyze the data. In the main model controlling for gender, age, body mass index, and time spent on social media, appearance envy and shame were associated with appearance comparisons on social media (R-2 = .54, p < .001). Appearance envy was also directly associated with online self-presentation (R-2 = .39, p < .001). The emotions were not significant correlates of appearance-related activity on social media. These findings were generally consistent for women and men, with women reporting higher levels of shame, envy, appearance comparison, online self-presentation, and time on social media compared to men. Based on these findings, strategies to reduce or manage appearance-related emotions of shame and envy are needed to protect from social media appearance preoccupation. With these efforts in place, the detrimental effects of social media use may be curbed.