A series of novel red phosphorescent polymers is successfully developed through Suzuki cross-coupling among ambipolar units, functionalized Ir-III phosphorescent blocks, and fluorene-based silane moieties. The photophysical and electrochemical investigations indicate not only highly efficient energy-transfer from the organic segments to the phosphorescent units in the polymer backbone but also the ambipolar character of the copolymers. Benefiting from all these merits, the phosphorescent polymers can furnish organic light-emitting diodes (OLEDs) with exceptional high electroluminescent (EL) efficiencies with a current efficiency ((L)) of 8.31 cd A(-1), external quantum efficiency ((ext)) of 16.07%, and power efficiency ((P)) of 2.95 lm W-1, representing the state-of-the-art electroluminescent performances ever achieved by red phosphorescent polymers. This work here might represent a new pathway to design and synthesize highly efficient phosphorescent polymers.