Two pyrene derivatives (PVPP and TPVPP) bearing 4-(2,2-diphenyl-vinyl)-phenyl side unit were developed for organic light-emitting diodes. Their photophysical, thermal, electrochemical, and electroluminescent properties as well as the film morphologies have been investigated in detail. Both of them exhibit high solid-state quantum yields, good thermal stability, and high glass-transition temperatures in the range of 127–150°C. In particular, it is found that multiple side units can significantly affect the electrochemical properties to improve the electron injection. The LUMO energy level of TPVPP is −2.76eV, which is very close to that of commonly used electron transport materials. The maximum luminance of OLED devices using TPVPP as an emitter layer is 103835cd/m2 with a maximum current efficiency of 5.19cd/A and a maximum power efficiency of 3.38lm/W.