We report the Fourier transform microwave spectra of four isotopologues of the hetero triad pyridine-Ar-Ne, formed by the combination of two isotopes of the nitrogen atom (14N and 15N) in pyridine with two isotopes of the rare gas (RG) atoms (20Ne and 22Ne), by using pulsed jet spectroscopy. We detected the conformer denoted [1,1], with the Ne and Ar atoms located one on each side of the ring plane. The [2,0] species, with the two RG atoms on the same side of the ring, was not observed. Ab initio MP2/6-311++G** calculations suggest the rotational spectrum of this species to be complicated by the presence of several almost equivalent minima, separated by very low barriers. Four structural van der Waals parameters, R(Ar), R(Ne), theta(Ar) and theta(Ne), which localize the RG atoms with respect to pyridine, are determined. The 14N nuclear quadrupole coupling constants are obtained for the isotopologues containing this nucleus.