Thin films of the light emitting conjugated polymer poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4- phenylene vinylene] (MEH-PPV) were drop cast under a high voltage DC electric field. The conformational changes and photophysical behavior were studied systematically via steady-state and time-resolved fluorescence measurements. A clear blue shift was observed in the fluorescence spectra for thin films of MEH-PPV cast under external high electric field, and this behavior is compared to low temperature fluorescence spectra. Emission polarization measurements indicate a level of alignment of the chromophoric units when films are cast within the electric field. Moreover, an emission wavelength dependence of the fluorescence decay profiles is observed from the films cast in the absence of the electric field, but no such behavior is seen for films cast in the presence of the electric field. We interpret these observations in terms of conformational changes occurring in the polymer under the influence of the electric field, reducing the occurrence of aggregate formation.