In this work, we report the preparation of a series of electroluminescent (EL) devices based on a high-performance polymer, poly(p-phenylene benzobisoxazole) (PBO), and their optoelectronic properties, which have been rarely explored. The device structure is optimised using a complex cathode structure of tris-(8-hydoxyquinoline) aluminium (Alq3)/LiF/Al. By tuning the thickness of the Alq3 layer, we improve the device efficiency dramatically in an optimized condition. Further analysis reveals that the Alq3 layer in the complex cathode structure acts as a hole blocker in addition to its electron-injection role. A green light emission with a maximum brightness of 8.7×103 cd/m2 and a moderate current efficiency of 4.8 cd/A is obtained. These values are the highest ever reported for PBO devices. The high operational stability demonstrated by the present device makes it a promising tool for display and lighting applications. A new material is added to the selection of polymers used in this field up to now.