Based on the molecular energy transfer mechanism, relative gains at 1067 and 637 nm wavelengths are achieved in thermally activated delayed fluorescence molecule AQ(PhDPA)2 and Nd complex with chelating phosphine oxide as ligands codoped polymer waveguides, with the excitation of low‐power UV light‐emitting diodes (LEDs) instead of traditional semiconductor lasers as pump sources. For AQ(PhDPA)2‐Nd(DBTTA)3(DBFDPO) (DBTTA = dibenzotetrathienoacene, DBFDPO = 4,6‐bis (diphenylphosphoryl) dibenzofuran) ‐codoped polymethylmethacrylate (PMMA), and AQ(PhDPA)2‐Nd(DBTTA)3(FDPO) (FDPO = 9,9‐bis (diphenylphosphorylphenyl) fluorene)‐codoped PMMA polymers with a mass ratio of 1:4 respectively, when they are spin‐coated as upper claddings, the relative gains of 2.2 and 1.8 dB cm−1 at 1067 nm are obtained in evanescent‐field waveguides with cross‐section of 4 × 8 µm2 under excitation of 300 mW 405 nm LED, and the gains of 3.9 and 4.9 dB cm−1 at 637 nm are achieved with pumping of 530 mW 450 nm LED respectively. By growing a 100 nm‐thick aluminum reflector with the waveguides, the optical gain at 1067 and 637 nm can be enhanced to 3.5 and 6.1 dB cm−1, corresponding to AQ(PhDPA)2‐Nd(DBTTA)3(DBFDPO) and AQ(PhDPA)2‐Nd(DBTTA)3(FDPO)‐codoped PMMA polymers, respectively.