Abstract A library of indolizines has been synthesized using poly (ethylene glycol)(PEG) as soluble polymer support. The PEG-supported pyridinium ylide reacted with alkenes or alkynes to give PEG-bound indolizines. Cleavage from the soluble polymer support was induced by KCN/MeOH to afford the indolizines. This synthetic method is simple, the reaction conditions are mild and the yields are high to excellent.