The potent two-phase hollow fiber electromembrane extraction technique coupled to gas chromatography mass spectrometry (HF-EME/GC-MS) was proposed for the determination of six types of carcinogen nitrosamines in sausages samples. Two steps of sample digestion were accomplished for the complete removal of fat globules and efficient release of target analytes. The extraction principle was based on electro-migration of target analytes via specific fiber to extraction solvent. 2-Nitrophenyl octyl ether (NPOE) was dexterously employed as both supported liquid membrane and extraction solvent, which is compatible with GC-MS. After the extraction process, the NPOE containing nitrosamines was directly injected to GC-MS without extra steps requirement to reduce analysis time. The consequences revealed that N-nitrosodiethylamine (NDEA) as the most potent carcinogen has the highest concentration in fried and oven-cooked sausages with 70% of red meat. The meat type and amount and also cooking process could significantly effect on nitrosamines formation.