The state of p-phenylphenol molecules in dioxane/water mixture, a commonly used reaction system for enzymatic polymerization of phenols and aromatic amines, was investigated by difference UV absorption spectroscopy and Fourier transform (FT) Raman spectroscopy. The aggregate of p-phenylphenols is found on the basis of the exciton peaks observed in difference UV absorption spectra. FT Raman spectroscopy demonstrates further that p-phenylphenol molecules aggregate together in "face to face" fashion. A simplified model is proposed for aggregation of p-phenylphenol molecules in dioxane/water mixture, which can elucidate the variation of the molecular weight of poly(p-phenylphenol) coupled in the reaction system.