Oxytocin (OT) has modulatory effects in both human behavior and in the brain, which is not limited in the specific brain area but also with the potential effect on connectivity with other brain regions. Evidence indicates that OT effects on human behavior are multifaceted, such as trust behavior, decrease anxiety, empathy and bonding behavior. For the vital role of mentalizing in understanding others, here we examine whether OT has a general effect on mentalizing brain network which is associated to the effect of related social behavioral and personality traits. Using a randomized, double-blind placebo-controlled group design, we investigate the resting-state functional magnetic resonance imaging after intranasal OT or placebo. The functional connectivity (FC) maps with seed in left/right temporoparietal junction (lTPJ/rTPJ) showed that OT significantly increased connectivity between rTPJ and default attention network (DAN), but decreased the FC between lTPJ and medial prefrontal network (MPN). With machine learning approach, we report that identified altered FCs of TPJ can classify OT and placebo (PL) group. Moreover, individual's empathy trait can modulate the FC between left TPJ and right rectus (RECT), which shows a positive correlation with empathic concern in PL group but a negative correlation in OT group. These results demonstrate that OT has significant effect on FC with lTPJ and rTPJ, brain regions where are critical for mentalizing, and the empathy concern can modulate the FC. These findings advance our understanding of the neural mechanisms by which OT modulates social behaviors, especially in social interaction involving mentalizing.