Pyrrolizidine　alkaloids　are　the　most　widely　distributed　natural　toxins,　and　pyrrolizidine　alkaloid-containing　herbal　medicines　are　probably　the　most　common　poisonous　plants　affecting　humans.　We　reported　pyrrolizidine　alkaloid-molecularly　imprinted　polymer　solid-phase　microextraction　for　the　selective　adsorption　of　toxic　pyrrolizidine　alkaloids　from　herbal　medicine.　A　sulfonic　compound,　sodium　allylsulfonate,　was　chosen　as　the　functional　monomer　to　interact　with　pyrrolizidine　alkaloids　through　strong　ionic　interaction.　To　avoid　template　leakage　and　for　the　aim　of　cost　saving,　a　relatively　cheap　dummy　template　was　used　for　the　fabrication　of　molecularly　imprinted　polymer-solid-phase　microextraction　fibers.　The　obtained　fibers　showed　selective　adsorption　ability　for　four　pyrrolizidine　alkaloids,　including　europine,　echimidine,　lasiocarpine,　and　heliotrine.　The　extraction　parameters,　such　as　extraction　time,　extraction　temperature,　shaking　speed,　elution　solvent　and　elution　time,　were　optimized.　Then　ultra　high　performance　liquid　chromatography　with　mass　spectrometry　coupled　with　molecularly　imprinted　polymer-solid-phase　microextraction　method　was　developed　for　the　fast　and　efficient　analysis　of　four　pyrrolizidine　alkaloids　from　the　model　herbal　plant　Farfarae　Flos.　The　established　method　was　validated　and　exhibited　satisfactory　accuracy　and　precision.　The　present　method　provides　an　innovative　and　fast　analytical　strategy　for　the　determination　of　trace　toxic　pyrrolizidine　alkaloids　in　complicated　samples.