For the first time, Excitation Emission Matrix (EEM) fluorescence spectroscopy was combined with parallel factor statistical analysis (PARAFAC) and applied to a set of 320 dry white wines of the Chardonnay grape variety. A four component PARAFAC model (C1, C2, C3 and C4) best explained the variability of fluorescence signatures of white wines. Subtle changes were observed in EEMs of white wines from two different vintages (2006 and 2007), where different concentrations of sulfur dioxide (0, 4, and 8 g·hL(-1)) were added to the grape must at pressing. PARAFAC results clearly indicated that sulfur dioxide added to the must subsequently influenced white wine chemistry into three distinct sulfur dioxide dose-dependent aging mechanisms. For both vintages, C1 and C2 were the dominant components affected by sulfur dioxide and likely reacting with phenolic compounds associated with some presumably proteinaceous material. Distinct component combinations revealed either SO2 dependent or vintage-dependent signatures, thus, showing the extent of the complex versatile significance underlying such fluorescence spectra, even after several years of bottle aging.