The hole transport in various poly(p-phenylene vinylene) (PPV) derivatives has been investigated in field-effect transistors (FETs) and light-emitting diodes (LEDs) as a function of temperature and applied bias. The discrepancy between the experimental hole mobilities extracted from FETs and LEDs based on a single disordered polymeric semiconductor originates from the strong dependence of the hole mobility on the charge carrier density. The microscopic charge transport parameters are directly related to the chemical composition of the analysed polymers. By chemically modifying the PPV, the hole mobility in both FETs and LEDs can be changed by orders of magnitude. For highly disordered PPVs it is demonstrated that the exponential density of states (DOS), which is used to describe the charge transport in FETs, is a good approximation of the tail states of the Gaussian DOS, which describes the charge transport in LEDs. Increase of the directional order in the PPV film enhances the mobility but also induces a strong anisotropy in the charge transport, thereby obscuring a direct comparison between sandwich and field-effect devices. (C) 2004 WILEY-VCH Verlag GmbH & Co. KGaA. Weinheim.