The synthesis of organic molecular anions in TMC-1 and IRC+10216 is investigated. Modelled C2H−, CN−, C3N−, C5N− and C7N− column densities are sufficiently great that these species might be observable in IRC+10216. Density-enhanced shells in the outer envelope of IRC+10216 are found to enhance the C2H− and CN− column densities by shielding these anions from destruction by UV radiation. From a newly-derived upper column density limit of 6.6 × 1010 cm−2 for C2H− in IRC+10216 we deduce the primary production mechanism for this anion to be C2H2 + H− ⇒ C2H− + H2. In TMC-1, due to the low radiative electron attachment rates calculated for C2H−, CN− and CH2CN−, these species have modelled column densities below the detection threshold. They could, however, be produced in reactions we have not yet considered.