A substantial body of research has assessed the effect of gender on face recognition; however, little is known about the effect of relationship status on face recognition. In this study, we assessed for the first time how relationship status impacts face recognition by asking 62 male and female participants to decide whether they had previously encountered faces of males and females. Participants were also asked to fill a socio-demographic variables questionnaire which included, among other information, question about their relationship status (i.e., single vs. in a relationship). A significant effect of relationship status on face recognition was observed only in males; namely, single males demonstrated higher face recognition than males in relationships, whereas similar face recognition was observed in single and in-relationship females. More specifically, single males demonstrated higher recognition for female than for male faces, whereas no differences were observed in single females, males in relationships, or in females in relationship. Single males seem to be motivated by mating opportunity and, thus, unlike single females or males and females in relationships, devote high attentional resources to processing faces of the opposite gender.