In this letter, an efficient hole-injection contact was achieved for the top-emitting polymeric light-emitting diodes (PLEDs). The anode has a structure of metal/molybdenum oxide/poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS). It has been found that hole injection was significantly improved by inserting a thin layer of MoO3 between aluminum and PEDOT:PSS. An ultraviolet photoelectron spectroscopy (UPS) was used to investigate the change of work function, and photovoltaic measurement confirmed that the improved hole injection is due to the reduction of barrier height, resulted from the addition of transition metal oxide. PEDOT:PSS layer was found necessary in anode structure to further enhance the hole injection and electroluminance efficiency. A peak power efficiency of 11.42lm∕W was achieved at current density of 1.2mA/cm2 for the white emission top-emitting PLEDs