Materials that exhibit visible luminescence upon X-ray irradiation show great potential in the medical and industrial fields. Pure organic materials have recently emerged as promising scintillators for X-ray detection and radiography, due to their diversified design, low cost, and facile preparation. However, recent progress in efficient radioluminescence has mainly focused on small molecules, which are inevitably associated with processability and repeatability issues. Here, a concise strategy is proposed to prepare radioluminescent polymers that exhibit multiple emission colors from blue to yellow with high brightness in an amorphous state by the radical copolymerization of negatively charged polyacrylic acid and different positively charged quaternary phosphonium salts. One of the obtained polymers exhibits excellent photostability under a high X-ray irradiation dosage of 27.35 Gy and has a detection limit of 149  nGy s^−  1. This performance is superior to that of conventional anthracene-based scintillators. Furthermore, by simply drop-casting a polymer methanol solution on a quartz plate, a transparent scintillator screen was successfully fabricated for X-ray imaging with a resolution of 8.7  line pairs mm^−  1. The pure organic phosphorescent polymers with a highly efficient radioluminescence were demonstrated for the first time, and the strategy reported herein offers a promising pathway to expand the application range of amorphous organic scintillators.