A solid-phase microextraction (SPME) analytical method has been developed for the determination of N-nitrosodi-n-butylamine (NDBA) and N-nitrosodibenzylamine (NDBzA) in hams that is based on: (a) isolation of the compounds by steam distillation, (b) SPME from the distillate headspace using a polyacrylate coated silica fibre and (c) determination by gas chromatography-thermal energy analyzer technique or confirmation by gas chromatography-mass spectrometry. Recoveries of both NDBA and NDBzA from hams spiked at 5 to 160 micrograms/kg levels ranged between 41 to 112%. The overall method is fast, sensitive (detection limits, 1 to 3 micrograms/kg), precise (within 10%) and fairly accurate (average recoveries 86% and 70%, respectively). The results obtained by this technique for seven ham samples agreed fairly well with those obtained by an existing method (r2 = 0.97). The new method is solventless, environmentally friendly and useful for rapid monitoring purposes.