The potential of excitation - emission matrices (EEM) measurements using classical right angle technique, in conjunction with chemometrics, was prospected for white wine classification with respect to their cultivar and geographical origin. For this purpose, wines belonging to four cultivars (Chardonnay, Pinot Gris, Riesling and Sauvignon) from two different countries (Romania and France) were investigated. The excitation – emission matrices were statistically processed using parallel factor analysis (PARAFAC). According to Soft Independent Modeling Classification Analogy (SIMCA) model, for cultivar differentiation, only 3 out of 107 wine samples (1 Pinot Gris (Romania); 1 Riesling (Romania) and 1 Sauvignon (France)) were misclassified while for geographical origin assessment, only 2 wines (1 Romania and 1 France) were misclassified. This study demonstrates the potential of excitation – emission fluorescence matrices spectroscopy using the classical right angle technique in wine authentication, without sample dilution.