A method and apparatus for transmitting a synchronization signal in a talk-around direct communication network is provided. The method includes: determining one of a plurality of second windows included in a first window as a synchronization reception window; selecting one of a plurality of synchronization slots included in the second windows as a first synchronization slot; transmitting a first synchronization signal through the first synchronization slot included in the second windows, excluding the synchronization reception window; detecting a second synchronization signal transmitted from other terminals using the first synchronization slot included in the synchronization reception window; and determining that a collision from amongst the synchronization signals has occurred based on the detection result.