A new method of ultrasonic assisted dispersive liquid-liquid microextraction (USADLLME) combined with flame atomic absorption spectrometry (FAAS) was developed to determinate trace gallium in vanadium titanium magnetite. In the proposed approach, 1-(2-pyridineazo)-2-naphthol was selected as a complexant of gallium and chlorobenzene was chosen as extractant. The processes of complex formation and microextraction were influenced by the following factors: dosage of complexant, complex pH, extractant and its dosage, extraction temperature and time, etc. Under optimal conditions, the linear range of working curve was 0.1–1 μg/mL with detection limit of 0.07 μg/mL, and the enrichment factor of gallium was 124. 0.5 μg/mL gallium standard solution was parallelly extracted using USADLLME and determined by FAAS for 7 times and the relative standard deviation (RSD) was 13.54%. The presented method was simple, fast, sensitive and low cost, which had been successfully applied to the quantitative determination of gallium in vanadium titanium magnetite with complex matrix.