• An off-design model with fluid decomposition parameters was established. • The influence of MM thermal decomposition on the ORC system was evaluated. • MM decomposition reduced the net power and efficiency of ORC system obviously. • MM decomposition may lead to incomplete evaporation and evaporator acid corrosion. The organic Rankine cycle (ORC) is an efficient power generation technology that has been widely used in renewable energy utilization and industrial waste heat recovery. The thermal stability of working fluids has a significant effect on the fluid selection and system design of ORC systems. In this study, an off-design model of an ORC system was established with hexamethyldisiloxane (MM) as the working fluid, and the effects of the MM thermal stability on the system were analyzed. The results showed that the effect of MM thermal decomposition on the cold source and working fluid pump was limited. The outlet temperature of the evaporator decreased with MM decomposition, which might lead to incomplete evaporation of working fluids and possible damage to the expander. The outlet temperature of the heat source also decreased with MM decomposition, which led to lower outlet temperatures than the acid dew point limit temperature. Both of these results can affect the safe operation of ORC systems. The net power and thermal efficiency of the system decreased with increasing thermal decomposition ratios of MM. The net power and thermal efficiency decreased by 7.48% and 10.72% respectively in the model of this study with a 10% decomposition ratio.