The solute–solvent interactions of hydrogen-bonded phenol–(H2O)n (n=3–5) clusters in electronic excited states were investigated by means of the time-dependent density functional theory (TDDFT) method. The geometric structures and IR spectra in ground state, S1 state, and T1 state of the clusters, were calculated using the density functional theory (DFT) and TDDFT methods. Only the ring form isomer, the most stable one of the cluster, was considered in this study. Four, five and six intermolecular hydrogen bonds were formed in phenol–(H2O)3, phenol–(H2O)4, and phenol–(H2O)5 clusters, respectively. Based on the analysis of IR spectra, it is revealed that the “window region” between unshifted and shifted absorption bands in both S1 and T1 state becomes broader compared with that in ground state for the corresponding clusters. Furthermore, two interesting phenomenon were observed: (1) with the anticlockwise order of the ring formed by the intermolecular hydrogen bonds in the H-bonded phenol–(H2O)n (n=3–5) clusters, the strengths of the intermolecular hydrogen bonds decrease in all the S0, S1 and T1 states; (2) upon electronic excitation, the smaller the distance between phenol and water is, the larger the change of intermolecular hydrogen bonds strength is. Moreover, the intermolecular hydrogen bond (phenolic OH is the H donor) is strengthened in excited state compared with that in ground state. But the intermolecular hydrogen bond (phenolic OH is the H acceptor) is weakened in excited state.