Electron attachment mass spectrometry (EAMS) has been developed to study mixtures of electronegative gases and plasmas. A quadrupole mass spectrometer (QMS) has been used to detect negative ions, formed from sampled species by attachment of low energy electrons. Varying the electron energy allows to collect the attachment cross section of the considered species. EAMS appears to be a very powerful technique to study the chemistry of electronegative gases. Unlike ionization mass spectrometry, where cross sections are low at the threshold and rather flat over a broad range of electron energies, attachment resonances are sharp and distinct. Also very limited fragmentation of the parent negative ion occurs, so a given molecule yields only a few different negative ions. This facilitates identification of components in a gas mixture. It is particularly advantageous for detection of large, fragile molecules, which break up after ionization, but can be easily transformed into large negative ions. Moreover, sensitive detection of active species is possible due to their relatively high attachment cross sections. A particularly important application of EAMS is the determination of an effective attachment cross section in a plasma. Recording this cross section allows to decide on the actual negative ion formation mechanism in the plasma environment, where active products of plasma conversion can significantly alter the negative ion production channels and consequently the whole balance of charged particles. Examples of EAMS applications to fluorocarbon gases and low-pressure radio-frequency plasmas are discussed. In aCF4discharge conversion of the parent gas into species likeC2F6andC3F8is easily visualized. The dominant mechanism of negative ion formation in the plasma is electron attachment to these minority species and not to the parent gas. Also larger polymers are readily formed in fluorocarbon plasmas. In aC2F6discharge molecules with up to ten carbon atoms (the mass limit of our apparatus) have been detected using EAMS. ©1998 American Institute of Physics.