Prosocial third-party punishment (3PP) is a punitive behavior against antisocial individuals, which might explain extended cooperativeness in humans. 3PP shows sexual dimorphism, being more frequent in men than in women. We studied whether sexually dimorphic features related to sexual hormones during development (facial dimorphism and 2D:4D) influence the tendency to engage in 3PP in a sample of 511 women and 328 men. After playing a Prisoner's Dilemma, participants had to decide whether to penalize the defection of a third player who had exploited his/her counterpart's cooperation. In line with previous studies, we observe that men are more prone to engage in 3PP than women. We find that this sex difference is due to cooperative men being more likely to punish than cooperative women. In addition, men with higher facial masculinity are less likely to engage in 3PP, whereas no features influence 3PP in women. We discuss the possibility that sex differences in the motivations and fitness implications underlying 3PP might be driving the observed results.