Floating-off film-transfer technique was used for the formation of semiconducting polymer multi-layers and the effect on the performance of polymer light-emitting diode (PLED) was studied. This method made it possible to avoid the solvent compatibility problem that was typically encountered in successive coating of polymeric multilayer by solution processing. F8BT and MEH-PPV were used for electron transporting layer (ETL) and for emissive layer, respectively. Current-voltage-luminance characteristics and luminescence efficiency results showed that the insertion of ETL by floating-off film-transfer technique followed by proper heat treatment resulted in a significant improvement in PLED operation due to its electron-transporting and hole-blocking abilities.