Iron (Fe) concentration is a crucial parameter for boiler safety. However, as the working fluid circulation circuits cross each other, and the working fluid operational parameters change over a wide range, monitoring the Fe content and evaluating pipeline safety are very difficult. The mass transfer process of Fe in a complex water circulation system was described by constructing a network calculation model of Fe mass transfer in the steam-water circulation system of a supercritical boiler. The distribution of Fe and the corrosion/deposition rate in the system was calculated and analyzed. The influence of a Fe mass disturbance in single or multiple equipment on the mass distribution of Fe in the system is discussed. The results show that model calculation data is close to the operational data. Under the effect of cyclic mass transfer, both the granular and dissolved Fe cannot be ignored. During one cycle, about 36% of Fe was deposited on the system tube; however, the deposition amount in the steam generator and superheater section accounted for 81.2% of the total deposition amount, and the rest was deposited in the low-temperature pipeline. The influence of disturbance on other nodes in the network is quite different, which provides the possibility of discriminating the location of the disturbance node. The research results can provide a theoretical reference for water chemical control and safety during the operation.