Eight extraction agents (water, methanol-water mixtures in various ratios, methanol, a 20 mmol l −1 ammonium phosphate buffer, and a methanol-phosphate buffer) were tested for the extraction of arsenic compounds from fruits, stems + leaves, and roots of pepper plants grown on soil containing 17.2 mg kg −1 of total arsenic. The arsenic compounds in the extracts were determined using high-performance liquid chromatography-hydride generation inductively coupled plasma mass spectrometry. Whereas pure water was the most effective extraction agent for fruits (87 ± 3.3% extraction yield) and roots (96 ± 0.6% extraction yield), the 20 mM ammonium phosphate buffer at pH 6 extracted about 50% of the arsenic from stems + leaves. Decreasing extractability of the arsenic compounds was observed with increasing methanol concentrations for all parts of the pepper plant. In pepper fruits, arsenic(III), arsenic(V), and dimethylarsinic acid (DMA) were present (25%, 37%, and 39% respectively of the extractable arsenic). Arsenic(V) was the major compound in stems + leaves and roots (63% and 53% respectively), followed by arsenic(III) representing 33% and 42% respectively, and small amounts (not exceeding 5%) of DMA and methylarsonic acid were also detected. Hence, for a quantitative extraction of arsenic compounds from different plant tissues the extractant has to be optimized individually.