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• Effect of the polymer M n on the TADF property was explored for the first time. • More compacted stacking and better energy transfer is observed in low M n polymers. • Low M n polymer achieves a record-high maximum EQE of 21.2 % at 628 nm. Thermally activated delayed fluorescence (TADF) polymers have made remarkable progress in solution processed organic light-emitting diodes (OLEDs) due to their superior film-forming stability. However, the effect of some factors such as the molecular weight and end groups on the optoelectronic properties is never explored so far. Herein, a set of the TADF conjugated polymers with the different number-average molecular weights (M n s) of 5.4, 24.8, 41.8 and 146.1 kg/mol are synthesized and their M n effect on the photoluminescence (PL) and electroluminescence (EL) is systematically investigated. The microstructure models of the spin-coated polymer films based on the M n and chain length are proposed for realizing efficient non-doped OLEDs. Low M n produces more compacted polymer chain stacking and smoother film morphology, leading to restricted non-radiative loss and more effective energy transfer. In particular, the polymers with low M n s of 5.4 and 24.8 kg/mol achieve the higher PL quantum yields and more efficient reverse intersystem cross from triplet to singlet excited state, as well as the record external quantum efficiencies of 21.2 % and 18.4 % with the EL emission peaks over 620 nm. In contrast, the PL and EL performances eventually deteriorate with further increasing M n s due to the sparser chain stacking and larger phase separation. The results show that the lower M n s enable the rigid polymers to form perfect amorphous films and render the luminescent unit more uniform distribution, similar to the classical doped systems, improving the EL behaviors of the polymers. [ABSTRACT FROM AUTHOR]