Ultra-fine dry powder extinguishing agent (UDPEA) is a promising alternative to Halon agents in aviation firefighting. The formulation of UDPEAs should balance environmental friendliness and practical engineering requirements, including high extinguishing efficiency, excellent flowability, and prolonged anti-reignition. This study investigates the effects of three modification methods (single perfluorooctyl triethoxysilane (FOTS), single N-(3-Triethoxysilylpropyl)perfluoro(2,5-dimethyl-3,6-dioxanonanoyl)amide (PFPE), and a combination of FOTS and PFPE at various mass ratios (2.0:0.4, 1.6:0.8, 1.2:1.2, 0.8:1.6, 0.4:2.0) (g)) on the performance of sodium bicarbonate-based UDPEA. The results indicate that using FOTS or PFPE alone improves the water and oil contact angles, but still fails to meet the required hydrophobicity and oleophobicity standards, and it also reduces the flowability and fire-extinguishing capability. A combination of FOTS and PFPE at the 1:2 ratio yields the best performance, with the water and oil contact angles of 145.169° and 143.542°, respectively, the lowest flowability index (0.224), minimal extinguishing concentration and time (14.183 g/m3 and 1.976 s, respectively), which is only 52.7% and 68.3% of those of the unmodified UDPEA's (26.927 g/m3 and 2.893 s), and the longest anti-reignition time (68.5 s). In addition, the fire-extinguishing mechanisms (chemical inhibition and physical heat absorption) and anti-reignition mechanisms of the modified UDPEA (with the FOTS to PFPE ratio of 1:2) were revealed. This research aims to design an eco-friendly, high-performance UDPEA as an effective substitute for Halon extinguishing agents. These findings can provide valuable insights for evaluating and selecting aviation fire-extinguishing agents.