For radioactive aerosol samples collected on glass fiber filter membranes, this study utilized ammonium bifluoride (NH4HF2) aqueous solution to dissolve the glass fiber filter membranes and recover plutonium in the samples through fluoride co-precipitation. NH4HF2 is a corrosive solid compound with a low melting point and high solubility in water. The molten and aqueous solutions of NH4HF2 have excellent corrosive effects on silica and oxides of plutonium and uranium. After the glass fiber filter membrane undergoes three steps of NH4HF2 dissolution, centrifugation to remove silicon and alcohol, and fluoride precipitation dissolution, 0.5 ml of small-volume AGMP-1M resin is used to separate and purify plutonium isotopes, and then ICP-QQQ is utilized to accurately measure plutonium isotopes at the fg/g. Experiments show that this method can rapidly dissolve glass fiber filter membranes in NH4HF2 solution in disposable plastic centrifuge tubes and effectively recover plutonium isotopes. The entire process does not require high-temperature equipment such as muffle furnaces, microwave digestion instruments, or electric hot plates, and is simple, fast, and safe to operate. Compared with traditional high-temperature strong acid digestion methods, such as microwave digestion, it has obvious technical advantages. When NH4HF2 is used to pre-treat glass fiber samples, the recovery rate of plutonium is no less than 75.9%. When 8 aerosol samples are processed per batch, the pre-treatment of aerosol samples takes less than 1.5 h, column separation takes less than 1 h, and ICP-QQQ measurement takes less than 1 h. The minimum detectable concentration (MDC) for 239Pu and 240Pu were 4.8 × 10–4 mBq/m3 and 1.9 × 10–3 mBq/m3, respectively.