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Near-infrared (NIR) spectrophotometers with different optical arrangements were used to measure the diffusely reflected electromagnetic radiation of different types of food additives in polyethylene (PE) foils. Eight compounds, frequently used in food process – but also in other industries –, were measured by different NIR spectrophotometers. The detected (‘as is’) and mathematically transformed (by scatter correction, second derivative combined with smoothing) NIR spectra were processed with multivariate data analysis (MDA). In this matter, unsupervised methods like principal component analysis (PCA) and cluster analysis (CA) were used, which techniques do not require prior information and reference measurements. The aim of the present study was to distinguish food additives by the help of the applied chemometric methods based on NIR spectra detected via the PE foils. Results indicated that distinction of different food additives and compounds with NIR methods is possible not only with the conventional sample preparations and handlings, but also without breaking the packaging.