AbstractRecently, 1,2‐dehydropyrrolizidine alkaloid (PA) ester alkaloids, found predominantly as their N‐oxides (PANOs, pyrrolizidine N‐oxides), have been reported in both honey and in pollen obtained directly from PA plants and pollen loads collected by bees, raising the possibility of health risks for consumers of these products. We confirm these findings in regard to floral pollen, using pollen collected directly from flowers of the known PA plants Senecio jacobaea, S. vernalis, Echium vulgare and pollinia of Phalaenopsis hybrids, and we extend analyses of 1,2‐unsaturated PAs and 1,2‐unsaturated PANOs to include bee‐pollen products currently being sold in supermarkets and on the Internet as food supplements. PA content of floral pollen ranged from 0.5 to 5 mg/g. The highest values were observed in pollen obtained from Senecio species. Up to 95% of the PAs are found as PANOs. Detailed studies with S. vernalis revealed unique PA patterns in pollen and flowers. While seneciphylline was the most prominent PA in S. vernalis pollen, the flowers were dominated by senecionine. To analyze trace amounts of 1,2‐unsaturated PAs in pollen products, our previously elaborated method consisting of strong cation exchange‐SPE, two reduction steps followed by silylation and subsequent capillary high‐resolution GC‐MS using SIM mode was applied. In total, 55 commercially available pollen products were analyzed. Seventeen (31%) samples contained 1,2‐unsaturated PAs in the range from 1.08 to 16.35 μg/g, calculated as retronecine equivalents. The 1,2‐unsaturated PA content of pollen products is expressed in terms of a single sum parameter and no background information such as foraged plants, pollen analysis, etc. was needed to analyze the samples. The detection limit of overall procedure and the reliable quantitation limit were 0.003 and 0.01 μg/g, respectively.