The hole transport in the amorphous poly(2-methoxy-5-(3',7'-dimethyloctyloxy)-p-phenylene vinylene) (OC1C10-PPV) and in the more ordered poly[2,5-bis(3',7'-dimethyloctyloxy)-p-phenylene vinylene] (OC10C10-PPV) has been investigated both in field-effect transistors (FETs) and light-emitting diodes (LEDs) as function of temperature and applied voltage. From J-V measurements on LEDs a difference of 15x has been found in the hole mobility between OC1C10-PPV and OC10C10-PPV. In FETs the dependence of the field-effect mobility on the carrier density is much stronger in OC1C10-PPV than in OC10C10-PPV. These differences in the mobility in both FETs and LEDs are determined by the difference in microscopic transport parameters between the two materia...