As members of a social species, we spend most of our time interacting with others. In interactions, we tend to mutually align our behavior and brain responses to communicate more effectively. In a semi-computerized version of the Rock-Paper-Scissors game, we investigated whether people show enhanced interpersonal neural synchronization when making explicit predictions about others’ actions. Across four experimental conditions, we measured the dynamic brain activity using the functional near-infrared spectroscopy (fNIRS) hyperscanning method. Results showed that interpersonal neural synchrony was enhanced when participants played the game together as they would do in real life in comparison to when they played the game on their own. We found no evidence of increased neural synchrony when participants made explicit predictions about others’ actions. Hence, neural synchrony may depend on mutual natural interaction rather than an explicit prediction strategy. This study is important, as it examines one of the presumed functions of neural synchronization namely facilitating predictions.