This study presents a novel strategy for the synthesis of intrinsic polymers with long-lived room-temperature phosphorescence (RTP) and white afterglow. By covalently coupling different conjugated chromophores with poly(acrylic acid-N-succinimide ester) (PAA-NHS) through a one-pot reaction, pure polymers with various colors of RTPs are obtained. The highest phosphorescence quantum yield of 14.7% is achieved in PAPHE. The afterglow colors of these polymers can be modulated from blue to red by adjusting the chromophore ratios. Notably, the polymer TPAP-514 exhibits a white afterglow at room temperature with chromaticity coordinates (0.33, 0.33) when the chromophore ratios are optimized. Systematic studies confirm that the emission originates from the superposition of different triplet excited states of the three chromophores. The potential applications of these polymers in light-emitting diodes (LEDs) and dynamic anti-counterfeiting are explored. This work provides a new approach for constructing RTP platforms in intrinsic polymer systems.This study presents a novel strategy for the synthesis of intrinsic polymers with long-lived room-temperature phosphorescence (RTP) and white afterglow. By covalently coupling different conjugated chromophores with poly(acrylic acid-N-succinimide ester) (PAA-NHS) through a one-pot reaction, pure polymers with various colors of RTPs are obtained. The highest phosphorescence quantum yield of 14.7% is achieved in PAPHE. The afterglow colors of these polymers can be modulated from blue to red by adjusting the chromophore ratios. Notably, the polymer TPAP-514 exhibits a white afterglow at room temperature with chromaticity coordinates (0.33, 0.33) when the chromophore ratios are optimized. Systematic studies confirm that the emission originates from the superposition of different triplet excited states of the three chromophores. The potential applications of these polymers in light-emitting diodes (LEDs) and dynamic anti-counterfeiting are explored. This work provides a new approach for constructing RTP platforms in intrinsic polymer systems.