The synthesis of trifluoromethylthiolated aliphatic acid derivatives by Pd-catalyzed C(sp(3))-H bond functionalization was developed. Using a bidentate directing group, the direct and selective introduction of a SCF3 moiety was possible on a range of amides with remarkable selectivity for C(sp(3))-centers with an electrophilic SCF3 source and pivalic acid as an additive. This work constitutes an example of the unactivated C(sp(3))-SCF3 bond formation by C-H activation offering a new access to relevant molecules.