In daily life, trust is important in interpersonal interactions. However, little is known about interpersonal brain synchronization with respect to trust; in particular, the differences between individuals with and without siblings are not clear. Therefore, this study applied functional near-infrared spectroscopy hyperscanning in a sequential reciprocal-trust task. We divided pairs of participants (strangers) into two groups according to their only-child status. The two strangers interacted with one another in an online trust game while their brain activities in the medial prefrontal cortex (mPFC) and the right temporoparietal junction (rTPJ) were measured. The behavioral results revealed that compared with the non-only-child group, the only-child group exhibited lower repayment, less reciprocation, and less cooperative decisions during the process. In addition, the brain imaging results showed that the interpersonal synchronization of the mPFC in the only-child group was significantly weaker than that in the non-only-child group. Our findings demonstrate neurobehavioral support for the only-child effect in terms of the trust by revealing that an only child shows less trust than does a non-only-child, resulting in lower inter-brain coherence.