Conjugated polar polymers, in which the conjugated backbones are chemically anchored with functional polar side groups, can be processed with water/alcohol solvents, and thus multilayered device architectures can be easily realized via sequential solution processing of the toluene-soluble emissive polymer and alcohol-soluble electron-transporting polymer without intermixing. Regarding their use in organic optoelectronic devices, the success in achieving efficient charge injection and intimate contact between metal electrodes and organic semiconductors is very vital for enhancing the device performance. In this short review, it gives a brief review to neutral alcohol-soluble phosphonate-functionalized polyfluorene, mainly concerning the electronic structure at the phosphonate-functionalized polyfluorene/aluminum cathode interface and its successful application in multilayered polymer optoelectronic devices including polymer light-emitting diodes and polymer solar cells.