In this letter, we present the results of the study of the hydrogen bond network of Poly(4-vinylphenol) (PVPh) by using Born-Oppenheimer molecular dynamics. The polymeric structure and IR spectra of PVPh result from the presence of hydrogen bonds between the hydroxyl group. The presented study focuses on the analysis of changes in the network of conjugated hydrogen bonds observed in Poly(4-vinylphenol). The hydroxyl groups form conjugated hydrogen bonds in separate domains. The ab initio molecular dynamics gave us a possibility to understand the stabilization role of the hydrogen bond in the polymer material. Additionally, the quantization of nuclear motion has been performed.