Structural and conformational properties of two sulfenyl derivatives, trifluoromethanesulfenyl acetate, CF3S-OC(O)CH3(1), and trifluoromethanesulfenyl trifluoroacetate, CF3S-OC(O)CF3 (2), were determined by gas electron diffraction, vibrational spectroscopy, in particular with IR (matrix) spectroscopy, which includes photochemical studies, and by quantum chemical calculations. Both compounds exist in the gas phase as a mixture of two conformers, with the prevailing component possessing a gauche structure around the S-O bond. The minor form, 15(5)% in 1 and 11(5)% in 2 according to IR(matrix) spectra, possesses an unexpected trans structure around the S-O bond. The C=O bond of the acetyl group is oriented syn with respect to the S-O bond in both conformers. UV-visible broad band irradiation of I and 2 isolated in inert gas matrixes causes various changes to occur. Conformational randomization clearly takes place in 2 with simultaneous formation of CF3SCF3. For I the only reaction channel detected leads to the formation of CH3SCF3 with the consequent extrusion Of CO2. Quantum chemical calculations (B3LYP/6-31G* and MP2 with 6-31G* and 6-311G(2df,pd) basis sets) confirm the existence of a stable trans conformer. The calculations reproduce the conformational properties for both compounds qualitatively correct with the exception of the B3LYP method for compound 2 which predicts the trans form to be prevailing, in contrast to the experiment.