Since the COVID-19 outbreak, the use of disposable plastics has rapidly increased along with the amount of plastic waste. During fragmentation, microplastics and other chemical substances contained in plastics are released. These then enter humans through food which could be problematic considering their hazardous potential. Polystyrene (PS), which is widely used in disposable containers, releases large amounts of microplastics (MPs), but no studies have investigated the release mechanisms of PS-MPs and simultaneously exposed contaminants. Therefore, in this study, the effects of pH (3, 5, 7, and 9), temperature (20, 50, 80, and 100 °C), and exposure time (2, 4, 6, and 8 h) on MPs release were systematically examined. A quantitative/qualitative study of MPs and styrene monomers was performed using microscopy-equipped Fourier-transformed infrared spectroscopy and gas chromatography-mass spectrometry. The release of PS-MPs (36 items/container) and simultaneously exposed pollutants (SEP), such as ethylene glycol monooleate (EGM), was highest at pH 9, 100 °C, and 6 h, which was proportional to the test temperature and time. Under the same conditions, 2.58 μg/L of styrene monomer migrated to the liquid food simulants. The fragmentation was proceeded by oxidation/hydrolysis and accelerated by increased temperature and exposure time. The strong positive correlation between PS-MPs and SEPs releases at pH and temperature indicates that PS-MPs and SEPs follow the same release process. However, a strongly negative correlation between PS-MPs and styrene monomers at the exposed time shows that styrene migration does not follow the same release process, but does its partition coefficient.