The invention discloses a phosphorus organic light-emitting diode with an NP-type composite hole injection layer and a fabrication method of the phosphorus organic light-emitting diode, and belongs tothe technical field of organic light-emitting devices. The organic light-emitting diode sequentially comprises a substrate layer, a hole injection layer, a hole transmission layer, an ultrathin light-emitting layer, an electron transmission layer, an electron injection layer and a negative electrode from bottom to top, wherein the hole injection layer is an NP-type composite hole injection layerand comprises an N-type semiconductor material C60 layer and a P-type semiconductor material MoO3 layer, and the material of the ultrathin light-emitting layer is a phosphorus organic material. According to the organic light-emitting diode and the fabrication method thereof, the C60/MoO3 composite structure is introduced as the hole injection layer, the hole injection capability of the device is improved, the energy level barrier between a positive electrode layer and the light-emitting layer is reduced, the driving voltage is reduced, so that the light-emitting efficiency of the device is improved; and meanwhile, the organic light-emitting diode employs a non-doped structure, the fabrication process can be simplified, the organic light-emitting diode is high in repeatability, and production on a large scale is easily achieved.