Ferroptosis has close association with Golgi apparatus (GA), and revealing GA polarity fluctuations during ferroptosis is critical for in-depth studying biological functions of GA for ferroptosis. Herein, we disclosed the fluctuations of GA polarity during the course of ferroptosis by a GA-targeting polarity-sensitive probe (GA-P), for the first time. The probe GA-P used a D-π-A-π-D framework to respond to GA polarity, and employed myristamide as GA-targeting group. Theoretical calculations indicated that dual ICT processes occurred after the transition of GA-P to excited state. GA-P mainly distributed in GA instead of the other organelles including ER and lysosome, and exhibited excellent GA-targeting ability. Imaging data demonstrated that ferroptosis can noticeably raise the GA polarity in the cells stimulated with erastin. Furthermore, like to the traditional ferroptosis inhibitors (Fer-1, DFO, et al.), dihydrolipoic acid and rutin could impede the significant fluctuations of GA polarity during ferroptosis.