The hydration structures of 3-aminopyridine (3AP)-(H2O) (n = 2-4) in supersonic jets have been investigated by measuring the electronic and vibrational spectra with the aid of quantum chemical calculations. The S-1-S-0 electronic transition of 3AP (H2O)(2) is observed at a slightly red-shifted position from 3AP (H2O)(1), while further hydration induces drastic red shifts and complicated vibrational structures. We assign the cluster structures of 3AP (H2O)(2) as a cyclic structure composed of the homodromic hydrogen bond (H-bond) chain connecting the pyridyl CH bond acting as the proton donor toward a pyridyl nitrogen acceptor. For 3AP (H2O)(n) (n = 3, 4), on the other hand, the initial donor site in the H-bond network changes from a pyridyl CH group to an amino group. The observed red shift derived from H-bond network switching can be reproduced very well with the S-1-S-0 origin band estimation obtained by applying geometry optimization and subsequent harmonic vibrational analysis of (TD-)DFT calculations to each electronic state of the isomer structure. It is suggested that the drastic red shift of the electronic transition upon H-bond network switching is due to a much more stabilized "quinoid-like" structure in the pi pi* state by the H-bond formation of an amino group.