The novel selenocarboxylic Se-acids, HCF2C(O)SeH and ClCF2C(O)SeH, were prepared by treating the corresponding carboxylic acids with Woollins' reagent. The boiling points were extrapolated from the vapor pressure curves to be 364 and 359 K for HCF2C(O)SeH and ClCF2C(O)SeH, respectively. Both compounds are unstable at ambient temperatures and decompose to the corresponding seleno anhydrides and release of H2Se. Hydrolysis results in formation of the carboxylic acids and hydrogen selenide, while diselenides presumably are obtained by oxidation. The conformational properties of these acids were studied by vibrational spectroscopy in combination with ab initio and DFT methods. IR vapor-phase spectra, Raman spectra of the neat liquids, and IR spectra of the Ar-matrix-isolated compounds deposited at two different nozzle temperatures were interpreted in terms of quenching conformational equilibria. The most stable structure of both acids was found to be syn-gauche in equilibrium with a second anti-syn form in HCF2C(O)SeH and with another two conformers, anti-gauche and anti-syn, in ClCF2C(O)SeH.