A new family of neutral alcohol-soluble small molecular materials comprised of electron-rich triphenylamine (TPA) and fluorene featuring phosphonate side chains (FEP) is reported, namely 3TPA-FEP, 2TPA-2FEP and TPA-3FEP, which have different TPA and FEP contents. Due to their good solubility in polar solvents like alcohol, multilayer devices can be fabricated by a wet process from orthogonal solvents. Polymer light-emitting devices with these materials as a cathode interlayer and Al as the cathode show greatly enhanced efficiencies in contrast to control devices without such a cathode interlayer, and their efficiencies are comparable with or even higher than devices with the low work-function metal Ba/Al as the cathode. In addition, high-performance polymer solar cells based on the poly[N-9''-hepta-decanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT):[6,6]-phenyl C71-butyric acid methyl ester (PC71BM) system are also achieved with power conversion efficiencies of 7.21%, 6.90% and 6.89%, by utilizing 3TPA-FEP, 2TPA-2FEP and TPA-3FEP as the cathode interlayer, respectively. These efficiencies are also much higher than those for control devices without the cathode interlayer. Although TPA is well-known as a hole-transport unit, the current findings indicate that alcohol-soluble TPA-based small molecules are also a promising cathode interlayer for both electron injection and extraction.