The synchronous fluorescence, first-order and second-order-derivative synchronous fluorescence spectra of BaP in cigarette mainstream smoke were studied. It was indicated that the second-order-derivative synchronous fluorescence spectrum could decrease the disturbances of BaP homologous compounds and background of sample. Hereby the present paper introduces a new method to determine BaP in cigarette mainstream smoke by solid-phase-extraction second-order-derivative synchronous fluorescence. The detection limit is 0.2 ng x mL(-1), the average recoveries of BaP are 80.2%-86.2%, and the RSD is 2.64%-3.02%.