AbstractSolvent effects on the nitrogen NMR shieldings of indolizine and three azaindolizines are presented for a range of thirteen solvents. The results are discussed in terms of hydrogen‐bonding an solvent polarity effects. ‘Pyridine‐type’ nitrogen atoms show a much larger range of solvent effects than do ‘pyrrole‐type’ nitrogens; solvent to solute hydrogen bonding is the dominant contribution to the changes in shielding for the ‘pyridine‐type’ nitrogen atoms as the solvent is varied. Solvent polarity effects are important for both types of nitrogen atom in azaindolizines and can be attributed to a solvent‐induced electronic charge separation between the nitrogen atoms concerned.Quantum chemical calculations involving the solvaton model are used to provide supporting evidence for the importance of solvent polarity effects on nitrogen shieldings in azaindolizines.