Diphenylbutadiene (DPBD) is an optical brightener incorporated into a wide range of polymeric materials. Framed in the FOODMIGROSURE project, it was chosen as a model migrant to study the migration kinetics from polymeric materials in relevant foodstuffs. An analytical method was developed and optimized for the DPBD determination in foods. The sample preparation procedure uses both hexane and acetonitrile as extraction solvents, followed by high-performance liquid chromatography (HPLC) analysis. HPLC analysis was performed using UV detection at a wavelength of 330 nm, and fluorescence detection achieved with excitation and emission wavelengths of 330 and 375 nm, respectively. Good linearity and recovery were achieved. Data are reported.