Tattooing is a widespread process of puncturing pigments into skin, whereas the resulting concentration inside the skin remains unknown. Many tattoo colorants are organic pigments, such as azo pigments, manufactured for other uses. To remove tattoos from skin, laser pulses at very high intensities are applied to the skin to destroy the tattoo pigments. Recent investigations have shown that several azo compounds are cleaved by laser light leading to potentially toxic or carcinogenic compounds. To assess the risk of tattooing and laser treatment of tattoos, the concentration of the pigments and their decomposition products in the skin must be determined. Therefore, an extraction method was established to determine the concentration of tattoo pigments and decomposition products quantitatively. The extraction of two widely used azo compounds, Pigment Red 22 and Pigment Red 9, and their laser-induced decomposition products, 2-methyl-5-nitroaniline, 4-nitrotoluene, 2,5-dichloraniline, and 1,4-dichlorobenzene, was accomplished using recovery experiments and HPLC-DAD technology. Despite the poor solubility of the pigments, a nearly complete recovery from aqueous suspension (> 92%) or lysed skin (> 94%) was achieved. The decomposition products were extracted from aqueous suspension or skin showing a recovery of up to 100%, except for the very volatile 1,4-DCB.