To obtain an efficient electrophosphorescent device, one needs to consider quenching of phosphor phosphorescence brought by the low triplet energy of the host because the exothermic energy transfer can effectively quench phosphor phosphorescence and markedly lower the device efficiency. Here, a facile approach of adding a branched alcohol (3-tert-butyl-2,2,4,4-tetramethylpentan-3-ol, ROH) into green emission phosphor-doped dialkoxyl-substituted poly(para-phenylene)s (PPPs) is demonstrated to effectively enhance shielding of triplet energy transfer to PPPs from the phosphor, resulting from a formation of self-assembly structure that block direct contact between phosphor and the main chains. The green electrophosphorescent device performance can be improved from 7.1 and 32.2 cd/A to 25.1 and 42 cd/A for PPP with dioctoxyl substituents (dC(8)OPPP) and with carbozole (Cz)-capped dialkoxyl-substituents (CzPPP), respectively. The latter result 42 cd/A is the highest record for green emission in polymer light emitting diode. This finding suggests that promotion of specific electro-optical properties for small molecule and polymer can be obtained through a self-assembling interaction in addition to chemical structure modification.