Abstract: GFAAS was applied to the determination of Ag in geological samples with novel dispersive liquid liquid microextraction using octanol as extractant. The optimized conditions found were as follows:① amount of octanol (extraction solvent) was 0.30 mL; ② amount of 2 g·L^-1 DPTU (complexing agent) ethanol solution was 1.0 mL; ③ amount of ethanol (dispersant) was 10 mL; ④ pH of sample solution was 3.0-7.0; ⑤ ashing temperature was 500℃; ⑥ atomization temperature was 1 700℃. Linear relationship between values of absorbance and mass concentration of Ag was kept in the range of 0.02-0.50 μg·L^-1, with detection limit (3s) of 4.7 pg. The proposed method was applied to the analysis of geological samples, giving results in consistency with the certified values with RSD's (n=5) in the range of 3.2%-6.8%.