Abstract The high yield synthesis of 3- and 4-(pentafluorosulfanyl)benzoic acid derivatives is described starting from the NO2-derivatives, which are reduced to the corresponding anilines. Then the NH2– group is converted to bromide and subsequently to the HC O moiety. The benzaldeydes are then oxidised to the corresponding benzoic acids. The X-ray structure of 3–SF5–C6H4–COOH is also reported.