Electrophosphorescence has been observed in doped polythiophene light-emitting diodes (LEDs) with poly(3-methyl-4-octylthiophene) [PMOT] as host and the phosphorescent compounds bis(2-phenylbenzothiazole) iridium acetylacetonate (BTIr) or platinum(II) 2,8,12,17-tetraethyl-3,7,13,18-tramethyl porphyrin (PtOX) as guest. The photoluminescence (PL) and electroluminescence (EL) of host–phosphorescent guest blends PMOT:BTIr (or PMOT:PtOX) showed the existence of energy transfer from host to guest, which were guest concentration-dependent. At a certain guest concentration, emission from host PMOT was completely quenched in both blends based LEDs, and this gave rise to electrophosphorescence. The PL from host PMOT in the PMOT:BTIr blend film could not be quenched completely but was totally quenched in PMOT:PtOX. This implies a more efficient energy transfer from PMOT to PtOX than that from PMOT to BTIr under optical excitation. Comparison of PL and EL showed that the mechanism of exciton formation at the guest site under electrical excitation was not identical for these two systems. Energy transfer was a dominating route for exciton formation in PMOT:PtOX-based LEDs; charge trapping effect additionally contributed to the formation of exciton at BTIr in PMOT:BTIr-based LEDs. This study demonstrates a new direction in which polythiophene can be a candidate as a host to realize electrophosphorescence in polymer light-emitting diodes (PLEDs). Authors further indicate that to optimize the performance of the polythiophe/phosphorescent complexes, LEDs proper polythiophenes with large bang gap are needed.