The formation of negative ions following electron impact to ethanol (CH(3)CH(2)OH) and trifluoroethanol (CF(3)CH(2)OH) is studied in the gas phase by means of a crossed electron-molecular beam experiment and in the condensed phase via Electron Stimulated Desorption (ESD) of fragment ions from the corresponding molecular films under UHV conditions. Gas phase ethanol exhibits two pronounced resonances, located at 5.5 eV and 8.2 eV, associated with a remarkable selectivity in the decomposition of the precursor ion. While the low energy resonance exclusively decomposes into O(-), that at higher energy generates OH(-) and a comparatively small signal of [CH(3)CH(2)O](-) due to the loss of a neutral hydrogen. CF(3)CH(2)OH shows a completely different behaviour, as now an intense feature at 1.7 eV appears associated with the loss of a neutral hydrogen atom exclusively occurring at the O site. The H(-) formation from the gas phase compounds is below the detection limit of the present experiment, while in ESD from 3 MonoLayer (ML) films of CH(3)CH(2)OH and CF(3)CH(2)OH the most intense fragment is H(-), appearing from a broad resonant feature between 7 and 12 eV. With CF(3)CH(2)OH, by using the isotopically-labelled analogues CF(3)CD(2)OH and CF(3)CH(2)OD it can be shown that this feature consists of two resonances, one located at 8 eV leading to H(-)/D(-) loss from the O site and a second resonance located at 10 eV leading to the loss of H(-)/D(-) from the CH(2) site.