Anthocyanins accumulate in plant vacuoles and are highly unstable at ambient temperatures, making them difficult to extract without denaturing their properties. This research aimed to determine a suitable extraction method and solvent composition for anthocyanin compounds. Australian blueberries were extracted using 12 different solvent compositions, with ultra-assisted extraction, Geno grinder, and Dounce grinder methods. The blueberry anthocyanin composition was analyzed against six commercial standards and quantified by mass spectrometry. The method was evaluated for linearity, food matrix effect, instrumental detection, and quantification limits. The total anthocyanin content ranged from 55.8 ± 0.7 mg/100 g to 84.9 ± 1.2 mg/100 g. The major anthocyanin detected was malvidin-3-glucoside. Ultra-sonication using methanol/water (80/20 v/v) at pH 3.0 produced the most effective homogenization with maximal extraction yield of anthocyanins. This study showed that the solubility of anthocyanin compounds is influenced by the solvent composition and extraction methods.