Topology structure and system parameters have a great influence on the dynamical behavior of dynamical networks. However, they are sometimes unknown or uncertain in advance. How to effectively identify them has been investigated in various network models, from integer-order networks to fractional-order networks with the same order. In the real world, many systems consist of subsystems with different fractional orders. Therefore, the structure identification of a dynamical network with different fractional orders is investigated in this paper. Through designing proper adaptive controllers and parameter updating laws, two network estimators are well constructed. One is for identifying only the unknown topology structure. The other is for identifying both the unknown topology structure and system parameters. Based on the Lyapunov function method and the stability theory of fractional-order dynamical systems, the theoretical results are analytically proved. The effectiveness is verified by three numerical examples as well. In addition, the designed estimators have a good performance in monitoring switching topology. From the practical viewpoint, the designed estimators can be used to monitor the change of current and voltage in the fractional-order circuit systems.