The photodetachment and stability of R-Mandelate, the deprotonated form of the RMandelic acid, was investigated by observing the neutral species issued from either simple photodetachment or dissociative photodetachment in a cold anions set-up. RMandalate has the possibility to form an intramolecular ionic hydrogen-bond between adjacent hydroxyl and carboxylate groups. The potential energy surface along the proton transfer (PT) coordinate between both groups (O-…H+…-OCO) features a single local minima, with the proton localized on the O- group (OH…-OCO). However, the structure with the proton localized on the –OCO group (O-…HOCO) is also observed because it falls within the extremity of the vibrational wavefunction of the OH…-OCO isomer along the PT coordinate. The stability of the corresponding radicals, produced upon photodetachment, is strongly dependent on the position of the proton in the anion: the radicals produced from the OH…-OCO isomer decarboxylate without barrier, while the radicals produced from the O-…HOCO isomer are stable.