Pyrrolizidine alkaloids (PAs) are phytotoxins, produced by more than 6,000 plant species. Bees forage on flowers of plants producing PAs, which leads to contamination of honey with the toxic compounds, through honey is known for its nutritional and medicinal properties. Pyrrolizidine alkaloids are toxic plant secondary metabolites produced as defense against herbivores by a wide variety of plants, mainly of the Boraginaceae, Asteraceae and Fabaceae families. Consumption of products contaminated with PAs may lead to hepatotoxic, carcinogenic, genotoxic and teratogenic effects in animals and humans. PAs are found in bee pollen when bees collect nectar and pollen from PA-producing plants, they enter the honey. In plant pollen, the PA content is in some cases higher than the one in leaves. PAs are a difficult class of toxins to investigate due to the large taxonomic diversity of PA-producing plants. Therefore the present investigation was aimed at extraction, isolation and purification of PAs by a simple and inexpensive method for the quantitative determination of PAs in Apis honey samples that makes the method applicable for the determination of PAs from food sources at toxic levels for consumers. By using only one solvent extraction of alkaloids from honey, the recovery percentage of senecionine (PA) is low (50.10%). By successive extractions, two times, with the same solvent, the senecionine retrieval percentage increases to 79.0%.