A strategy is proposed for the synthesis of intrinsic polymers with tunable, long-lived room-temperature phosphorescence (RTP). By covalently coupling different conjugated chromophores with poly(acrylic acid (AA)-AA-N-succinimide ester) (PAA-NHS) through a simple one-pot reaction, pure polymers with various color RTPs are obtained. Among these, PAPHE exhibits the highest phosphorescence quantum yield of 14.7%. The afterglow colors of the polymers can be modulated from blue to red by introducing different chromophores. Notably, the polymer TPAP-514 exhibits white afterglow at room temperature with chromaticity coordinates (0.33, 0.33) due to the three-primary-color mechanism. Systematic studies show that the emission arises from the superposition of different triplet excited states of the three components. The polymers have potential applications in light-emitting diodes (LEDs) and dynamic anti-counterfeiting. The strategy provides a new approach for constructing intrinsic polymers with diverse white-light emission RTPs. The study demonstrates that the phosphorescence of TPAP-514 originates from the superposition of triplet excited states of the three components. The polymers were synthesized by grafting different phosphorescent chromophores onto PAA-NHS. The resulting polymers exhibit long-lived RTPs with various colors, and TPAP-514 shows white afterglow. The study highlights the importance of covalent bonding in achieving stable and efficient RTP materials. The results indicate that the phosphorescence of TPAP-514 is due to the superposition of triplet excited states of the three components. The study provides a new strategy for the synthesis of intrinsic polymers with diverse white-light emission RTPs. The polymers were synthesized by grafting different phosphorescent chromophores onto PAA-NHS. The resulting polymers exhibit long-lived RTPs with various colors, and TPAP-514 shows white afterglow. The study highlights the importance of covalent bonding in achieving stable and efficient RTP materials.A strategy is proposed for the synthesis of intrinsic polymers with tunable, long-lived room-temperature phosphorescence (RTP). By covalently coupling different conjugated chromophores with poly(acrylic acid (AA)-AA-N-succinimide ester) (PAA-NHS) through a simple one-pot reaction, pure polymers with various color RTPs are obtained. Among these, PAPHE exhibits the highest phosphorescence quantum yield of 14.7%. The afterglow colors of the polymers can be modulated from blue to red by introducing different chromophores. Notably, the polymer TPAP-514 exhibits white afterglow at room temperature with chromaticity coordinates (0.33, 0.33) due to the three-primary-color mechanism. Systematic studies show that the emission arises from the superposition of different triplet excited states of the three components. The polymers have potential applications in light-emitting diodes (LEDs) and dynamic anti-counterfeiting. The strategy provides a new approach for constructing intrinsic polymers with diverse white-light emission RTPs. The study demonstrates that the phosphorescence of TPAP-514 originates from the superposition of triplet excited states of the three components. The polymers were synthesized by grafting different phosphorescent chromophores onto PAA-NHS. The resulting polymers exhibit long-lived RTPs with various colors, and TPAP-514 shows white afterglow. The study highlights the importance of covalent bonding in achieving stable and efficient RTP materials. The results indicate that the phosphorescence of TPAP-514 is due to the superposition of triplet excited states of the three components. The study provides a new strategy for the synthesis of intrinsic polymers with diverse white-light emission RTPs. The polymers were synthesized by grafting different phosphorescent chromophores onto PAA-NHS. The resulting polymers exhibit long-lived RTPs with various colors, and TPAP-514 shows white afterglow. The study highlights the importance of covalent bonding in achieving stable and efficient RTP materials.