Thin films of a divinyl derivative of tetraphenyldiaminobiphenyl DvTPD were prepared by vapor deposition followed by annealing. After annealing at 200°C for 1 h, the film became practically insoluble to organic solvents due to polymerization. Electrical characteristics of the films were measured by current-voltage measurement, time-of-flight measurement, and dielectric measurement. It was found that the hole mobility of DvTPD decreases when the film is polymerized. As a consequence of the decrease of hole mobility, carrier balance in the emissive layer of an organic light emitting diode (OLED) was improved, leading to a higher quantum efficiency and a pure emission spectrum. The dielectric measurement also confirmed the high thermal stability of the polymerized film.