AbstractCharge carrier mobility in poly(2‐methoxy,5(2′‐ethyl‐hexyloxy)‐p‐phenylene vinylene) (MEH‐PPV) films were measured as a function of temperature and electric field parallel and perpendicular to the substrate for devices prepared from different solvents and under different processing conditions. Bulk structural morphology was characterized by various X‐ray diffraction measurements such as wide angle, small angle and X‐ray reflection. Surface morphology was characterized using various scanning probe microscopic techniques. Mobilities were found to follow Gaussian disorder model (GDM) and to be highly anisotropic not only depending on the solvents used but also on the film preparation method such as spin‐coating or drop‐casting. While no direct correlation was found between charge carrier mobility and photoluminescence, charge transport parameters were correlated with structural morphology.