N1s binding energies for 36 pyridines substituted at the 2-, 3-, and 4-positions have been determined by X-ray photoelectron spectroscopy. The differences in BE relative to pyridine are analysed in terms of existing theoretical approaches (electrostatic, ground potential, and relaxation potential models) and compared with [Formula: see text] values calculated for analogous monosubstituted benzenes. One finds good correlations of [Formula: see text] with solution determined σ-substituent values although some substituent values deviate from the correlation probably due to solution effects which are not present in the gas phase. Correlations between [Formula: see text] and 14N nmr chemical shifts are poor, particularly for electron withdrawing substituents. The relationship between [Formula: see text] and gas phase basicity values (ΔG0) is good, and it appears as if the [Formula: see text] is more sensitive to the substituent than ΔG0. MINDO/3 calculations on the methoxypyridines and their conjugate acids employing full geometry optimizations are presented and analysed in order to determine the effect of geometric relaxation on the gas phase basicity.