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The ad hoc network may play an important part in future wireless communication systems. However, system synchronization of the ad hoc network is a big challenge due to the lack of a fixed infrastructure and the dynamically changing topology. A novel self synchronization algorithm is proposed for the ad hoc network based on TDMA; the network topology structure information is gathered in some assigned time slots to build a connected domain set and broadcast the system synchronization messages over the whole network. The system time slot cost of synchronization is about 16.7%, and the probability of a node being successfully synchronized is higher than 95% in typical network environments, as shown by simulation.