The performance of organic light-emitting devices (OLEDs) is strongly influenced by the electronic properties of the employed materials. In order to determine the effect of these materials' parameters, several different hole-transporting 1,3,5-tris(4-diphenylaminophenyl)benzenes (TDAPBs) were synthesised. These TDAPBs contained different substituents, different numbers of substituents and different positions of theses substituents. For the evaluation of the electronic properties, cyclic voltammetry was employed in order to determine the HOMO values, and time-of-flight (TOF) measurements to obtain the hole mobilities. OLEDs were prepared consisting of the TDAPBs blended in a polymer matrix, and of Alq3 as electron-conducting and light-emitting layer. These devices were investigated regarding their current density/voltage characteristics, efficiencies, onset voltages for electroluminescence, and lifetimes. For hole-transporting blend systems an exponential relationship between the current density and the HOMO levels of the TDAPBs was found. However, even though the HOMO values cover a range from −5.09 to −5.35 eV, no effects on the performance of the OLEDs were detected for electroluminescent two-layer systems. In this case the initial voltage seems to be a determining parameter for the behaviour of the devices during operation. Copyright © 1999 John Wiley & Sons, Ltd.