Copolymers of phosphafluorenes are obtained through Suzuki copolymerization. The phosphorus-containing copolymers show unique optical, electrochemical, and optoelectronic properties. Blue and white electroluminescence can be observed, depending on the modifications of the phosphorus atoms. It is the first time that conjugated polymers containing phosphafluorene have been prepared and used in PLEDs. Phosphafluorenes are new building blocks for conjugated oligomers and polymers.