The large global production of plastics and their presence everywhere in society and the environment have created a need for assessing chemical hazards and risks associated with plastic products. Plastics from polystyrene can release potentially toxic products (including styrene), particularly when heated. In this study we used a Fluo-Imager Analyser with software for spectral fluorescence signature (SFS) analysis. The objective of this study was to evaluate and compare the amount of styrene released into food and beverages by using SFS on a Fluo-Imager Analyser. Our results showed that concentrations of released styrene were in the range of 1.45–9.95 µg/L for hot water and 0.10–2.78 µg/L for room temperature water. The results indicate that this fluorescence diagnostic method is an effective tool for analysis of styrene released into food and beverages from polystyrene containers and cups, and could be useful in further investigations of styrene toxicity.