In this paper, the problem of structure-triggered asymptotical synchronization for nonidentical generalized stochastic systems with Markovian jumping parameter is investigated. Firstly, by designing a structure-triggered communication scheme, the optimal master system can be chosen for the slave system to synchronize. Furthermore, when the master system selected for the first time fails, the system can be promptly chosen again. Secondly, based on the sliding mode control approach and the linear matrix inequality technique, some sufficient conditions for synchronization of the nonidentical generalized stochastic systems are obtained. Finally, the effectiveness of the method is illustrated by two numerical examples.