Printing organic semiconductor inks by means of roll-to-roll compatible techniques will allow a continuous, high-volume fabrication of large-area flexible optoelectronic devices. The gravure printing technique is set to become a widespread process for the high throughput fabrication of functional layers. The gravure printing process of a poly-phenylvinylene derivative light-emitting polymer dissolved in a two solvent mixture on poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is studied. The surface tensions, contact angles, viscosities, and drying times of the formulations are investigated as a function of the solvent volume fraction and polymer concentration. The properties of the ink grant a homogeneous printed layer, suitable for device fabrication, when the calculated film leveling time is shorter than a critical time, at which the film has been frozen due to loss of solvent via evaporation. The knowledge obtained from the printing process is applied to fabricate organic light-emitting diodes (OLEDs) on flexible substrates, yielding a luminance of ≈5000 cd m−2.