A series of novel praseodymium (Pr)-bonded polymers with fluorene, phthalimide and phenanthroline moieties in the main chain were synthesized via the coordination reaction and palladium-catalyzed Suzuki coupling reaction. The resistive switching devices with the configuration ITO/Polymer/Al exhibited nonvolatile write-once-read-many-times (WORM) memory behavior. The introduction of Pr complex into the polymer main chain played a key role in the memory performance of the devices.