Electron transfer controlled hydrogen bonding was studied for a series of nitrobenzene derivative radical anions, working as large guest anions, and substituted ureas, including dihomooxacalixarene bidentate urea derivatives, in order to estimate binding constants (Kb) for the hydrogen-bonding process. Results showed enhanced Kb values for the interaction with phenyl-substituted bidentate urea, which is significantly larger than for the remaining compounds, e.g., in the case of 4-methoxynitrobenzene a 28-fold larger Kb value was obtained for the urea bearing a phenyl (Kb ∼ 6888) vs tert-butyl (Kb ∼ 247) moieties. The respective nucleophilic and electrophilic characters of the participant anion radical and urea hosts were parametrized with global and local electrodonating (ω(-)) and electroaccepting (ω(+)) powers, derived from DFT calculations. ω(-) data were useful for describing trends in structure–activity relationships when comparing nitrobenzene radical anions. However, ω(+) for the host urea structures lead to unreliable explanations of the experimental data. For the latter case, local descriptors ωk(+)(r) were estimated for the atoms within the urea region in the hosts [∑kωk(+)(r)]. By compiling all the theoretical and experimental data, a Kb-predictive contour plot was built considering ω(-) for the studied anion radicals and ∑kωk(+)(r) which affords good estimations.