Based on three-layer triangle network, the polygonal networks are established for mutually coupled semiconductor lasers. Firstly, the chaotic synchronization characteristics of the lasers in the three-layer triangle network are numerically analyzed and investigated. Then, the three-layer triangle network is extended to three-layer hexagonal network or even more complex polygonal network, and taking the first layer laser as the vertex laser for structural optimization, the proprieties of chaotic synchronization are studied between lasers in different layers for these complex structures. The results show that the lasers in three-layer triangle network, as well as in the three-layer hexagonal network or even more complex polygonal network formed by increasing side numbers of polygonal network, lasers except the apex can achieve chaotic synchronization in the same or different layers.