This study presents the development and validation of a precise analytical method for the speciation analysis of arsenic (As) compounds, including inorganic species [As(III) and As(V)] and organic species such as monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). The method employs anion-exchange high-performance liquid chromatography (AE HPLC) coupled with inductively coupled plasma-mass spectrometry (ICP-MS). To optimize the sample preparation process, microwave-assisted extraction (MAE) and heat-assisted extraction (HAE) techniques were evaluated and compared. Separation of all four arsenic species was achieved with baseline resolution within 10 min, utilizing an anion-exchange column and a mobile phase gradient of 0.5 and 5 mM ammonium carbonate with 3% (v/v) methanol at a pH of 9.3. The method validation followed the accuracy profile approach, employing six different food matrices analyzed in duplicate over six separate days within a 6-week period. The method demonstrated good intermediate reproducibility, with coefficients of variation (CV