Appearance modification practices are ubiquitous, serving to enhance physical attractiveness and accrue social advantages, including increased desirability as a potential mate. Facial cosmetics are frequently used for appearance modification, yet individual differences in makeup usage remain understudied. While makeup usage in women has been linked to traits like narcissism and extraversion, the broader association with Dark Triad traits and how personality influences makeup application across diverse social contexts were less explored. Here we examined these relationships in 1,410 Brazilian women (Mage = 29.9, SD = 10.35), who completed online Big Five and Dark Triad personality measures, reported their usual makeup usage habits, and detailed their makeup usage across different social scenarios. Results revealed makeup usage was positively associated with narcissism and extraversion, and negatively with psychopathy. Additionally, women used less makeup when alone (at home, exercises) and more in social settings, particularly for the first date. However, women with higher narcissism and neuroticism showed larger differences among low and high makeup usage situations, while individuals with higher psychopathy used makeup in similar frequencies among different situations. Further, (1) overall greater users of makeup scored higher on narcissism, conscientiousness, and agreeableness; (2) average users displayed lower psychopathy; and (3) lesser users reported lower narcissism and higher psychopathy. These findings underscore the nuanced relationship between makeup usage and personality, particularly highlighting the influence of narcissism. These findings contribute to the interplay between personality traits and makeup usage, considering interindividual differences and intraindividual variation in understanding cosmetic behaviors among women.