Visible spectral afterglow materials offer unprecedented potential for a myriad of applications due to their long luminescence characteristics, but it is still insufficient to prepare matrix-free materials with multicolor afterglow including the blue color. In this study, we successfully developed phosphorus and nitrogen codoped carbonized polymer dots (CPDs) with multicolor room temperature phosphorescence (RTP) including the blue color by microwave-assisted chemical reactions under different reaction time. After ceasing UV light, all four prepared CPDs were able to emit vivid RTP with a maximum absolute phosphorescence quantum yield (QY) of 59.41% and a maximum lifetime of about 1 s (yellow CPDs). With the increase of microwave reaction time, the RTP color of CPDs showed a gradual blue shift from yellow to blue. The reason why the RTP color of CPDs showed a gradual blue shift was the decrease of C═O units as the extension of the microwave reaction time. In view of their fascinating multicolor RTP properties, potential applications of the four CPDs in the field of anticounterfeiting painting were presented and demonstrated. This work would inspire other researchers to enrich multicolor afterglow materials.