In this work, we discuss the relative efficiency of the organic electroluminescent devices (OELDs) utilizing various fluorine-containing polyimides in hole transporting layer (HTL) in terms of the structure of the polyimides (PI) by molecular dynamics estimation. Materials for polyimides investigated in this study are; 1,2,4,5-benzentetracarboxylic dianhydride (PMDA), 4,4'-(hexafluoroisopropylidene) diphtalic anhydride (6FDA), 4,4'-oxydianiline (ODA), and 4,4'-(hexafluoroisopropylidene) dianiline (6FDAm). The devices used in this study consist of two organic layers, i.e. ITO-coated glass/TPD-dispersed polyimide/Alq3/Al devices. It was found that the EL efficiency of the OELDs is significantly affected by the molecular structure of polyimides as well as the contents of fluorine atoms in the PI. Molecular dynamics calculation proved that PMDA-6FDAm PI exhibits largest steric hindrance among the four PIs used in this work, due to the largest torsion of benzene rings.