The palladium catalysed hydroesterification of linear alkenes to obtain carboxylic esters in supercritical carbon dioxide is studied for the first time. Palladium complexes with phosphines containing -CF3 groups are used as catalyst precursors. For 1-hexene, conversions into the corresponding methyl esters up to 67% were obtained using [PdCl2(PhCN)(2)]/P(3,5-CF3C6H4)(3).