Resonant electron capture by aza and diaza derivatives of phenanthrene (7,8-benzoquinoline and 1,10-phenanthroline) and anthracene (acridine and phenazine) at incident free electron energies (Ee) in the range of 0-15 eV was studied. All compounds except 7,8-benzoquinoline form long-lived molecular ions (M-) at thermal electron energies (Ee ∼ 0 eV). Acridine and phenazine also form such ions at epithermal electron energies up to Ee = 1.5-2.5 eV. The lifetimes (τa) of M- with respect to electron autodetachment are proportional to the extent of aza-substitution and increase on going from molecules with bent geometry of the fused rings (azaphenanthrenes) to linear isomers (azaanthracenes). These regularities are due to an increase in the adiabatic electron affinities (EAa) of the molecules. The EAa values of the molecules under study were comprehensively assessed based on a comparative analysis of the measured τa values using the Rice-Ramsperger-Kassel-Marcus theory, the electronic structure analysis using the molecular orbital approach, as well as the density functional calculations of the total energy differences between the molecules and anions. The only fragmentation channel of M- ions from the compounds studied is abstraction of hydrogen atoms. When studying [M-H]- ions, electron autodetachment processes were observed, the τa values were measured, and the appearance energies were determined. A comparative analysis of the gas-phase acidity of the molecules and the EAa values of the [M-H]· radicals revealed their proportionality to the EAa values of the parent molecules.