The infrared (IR) spectra of the O-H stretching vibrations of pyridine-water clusters (Pyd)m(H2O)n, with m, n = 1-4, have been investigated with infrared-vacuum ultraviolet (VUV) spectroscopy under a jet-cooled condition. The time-of-flight mass spectrum of (Pyd)m(H2O)n+ by VUV ionization at ∼9 eV showed an unusual intensity pattern with very weak ion signals for m = 1 and 2 and stronger signals for m ≥ 3. This unusual mass pattern was explained by a drastic structural change of (Pyd)m(H2O)n upon the VUV ionization, which was followed by the elimination of water molecules. Among the recorded IR spectra, only one spectrum monitored, (Pyd)2+ cation, showed a well-resolved structure. The spectrum was analyzed by comparing with the simulated ones of possible stable isomers of (Pyd)2(H2O)n, which were obtained with quantum-chemical calculations. Most of the calculated (Pyd)2(H2O)n clusters had the characteristic structure in which H2O or (H2O)2 forms a hydrogen-bonded bridge between two pyridines to form the π-stacked (Pyd)2, and an additional H2O molecule(s) extends the H-bonded network. The π-stacked (Pyd)2(H2O)n moiety is very stable and is thought to exist as a local structure in a pyridine/water mixed solution. The Fermi resonance between the O-H stretch fundamentals and the overtones of the O-H bending vibrations in (Pyd)m(H2O)n was found to be less pronounced in the case of (Pyd)m(NH3)n studied previously.