AbstractThe energy transfer processes taking place in a single polymeric layer that enable the definition of the three primary colours (red, green and blue) in selected areas via photochemically induced emission tuning are discussed. The polymers used as hosts are two wide band gap polymers, PVK and a polyfluorenyl derivative. In the polymer matrix are dispersed the green emitter, 1‐(4′‐dimethyl‐aminophenyl)‐6‐phenyl‐1,3,5‐hexatriene (DMA‐DPH), the red emitter, 4‐dimethylamino‐4′‐nitrostilbene (DANS) and a photoacid generator (PAG). Upon irradiation, protons are released from the PAG and they react gradually with the two emitters, causing the blue shift of the green emitter fluorescence and the extinction of the red emitter fluorescence. Depending on the protonation extent, the relative concentrations of the emitters and the exposure dose the energy transfer processes occurring inside the matrix result in definition of different colour emitting areas. The understanding of the energy transfer processes with photoluminescence experiments is a necessary first step in order to rationalize the selection of suitable components enabling the definition of the three primary colours in OLEDs. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)