This paper quantitatively determined the migration level of benzo(a)pyrene (BaP) from paper cups into aqueous food simulants or fatty stimulants, under different conditions by second derivative constant-energy synchronous fluorescence spectrometry (DCESFS), which proved to be a method with high sensitivity and spectral resolution. The influences of food simulants, time and temperature on the relative migration percent(%) of benzo(a) pyrene were discussed. Results showed that the recoveries of this method ranged from 89.2% to 104.3%. The migration percent(%) of fatty stimulants was higher than that of aqueous simulants. Migration into hot water was also observed, while the migration into cool water was almost negligible. The relative migration percent(%) increased with the increase of time and temperature.