To examine the quenching of a triplet exciton by low triplet energy (E-T) polymer hosts with different chain configurations for high E-T phosphor guests, the quenching rate constant measurements were carried out and analyzed by the standard Stern-Volmer equation. We found that an effective shielding of triplet energy transfer from a high E-T phosphor guest to a low E-T polymer host is possible upon introducing dense side chains to the polymer to block direct contact from the guest such that the possibility of Dexter energy transfer between them is reduced to a minimum. Together with energy level matching to allow charge trapping on the guest, high device efficiency can be achieved. The extent of shielding for the systems of phenylene-based conjugated structures from iridium complexes follows the sequence di-substituted (octoxyl chain) in the para. position (dC(8)OPPP) is greater than monosubstituted (mC(8)OPPP) and the PPPs with longer side chains are much higher than a phenylene tetramer (P4) with two short methyl groups. Further, capping the dialkoxyl-susbstituents with a carbazole (Cz) moiety (CzPPP) provides enhanced extent of shielding, Excellent device efficiency of 30 cd/A (8.25%) for a green electrophosphorescent device can be achieved with CzPPP as a host, which is higher than that of dC(8)OPPP as host (15 cd/A). The efficiency is higher than those of high E-T conjugated polymers, poly(3,6-carbazole) derivatives, as hosts (23 cd/A). This observation suggests a new route for molecular design of electroluminescent polymers as a host for a phosphorescent dopant.