This study tested the hypothesis that individual differences in the activity of the orbitofrontal cortex, a region implicated in value-based decision-making, are associated with the preference for a person with a partner, which could lead to mate poaching. During functional magnetic resonance imaging (fMRI), male participants were presented with facial photographs of (a) attractive females with a partner, (b) attractive females without a partner, (c) unattractive females with a partner, and (d) unattractive females without a partner. The participants were asked to rate the degree to which they desired a romantic relationship with each female using an 8-point scale. The participants rated attractive females higher than unattractive females, and this effect was associated with ventral striatum activation. The participants also indicated lower ratings for females with a partner than for females without a partner, and this effect was associated with parietal cortex activation. As predicted, the participants characterized by higher orbitofrontal activity demonstrated a greater willingness to engage in a romantic relationship with females who have a partner compared with females who do not have a partner. These results are the first to provide a possible neural explanation for why certain individuals are willing to engage in mate poaching.