Phthalates used as plasticizers in the manufacture of household containers can potentially be transferred to foods that are stored or heated in these plastic containers. Phthalates are endocrine disruptor compounds (EDC) and are found in very low concentrations in foods, thus, highly sensitive analytical techniques are required for their quantification. This study describes the application of a new method developed for analyzing the migration of dibutylphthalate (DBP) and benzylbutylphthalate (BBP) from plastic food containers into liquid food simulants. This new method employs the technique of solid phase microextraction cooled with liquid nitrogen. The analysis was conducted by gas chromatography/mass spectrometry (GC/MS) using a polyacrylate fiber. Ultrapure water was used as a simulant for liquids foods, and both new and used plastic containers were placed in a domestic microwave oven for different periods of time at different power levels. The limits of detection for DBP and BBP were 0.08 µg/L and 0.31 µg/L, respectively. BBP was not found in the samples that were analyzed. DBP was found in concentrations ranging from <LOQ to 7.5 µg/L. In general, an increase in migration was observed in containers that were used for a prolonged time, which correlated with increasing heating time.