A series of cross-linked thin films were prepared via thiol-ene click chemistry from 4-phenylethenyl end-capped tunable band gap conjugated polymers with different photoemission. We demonstrate that the emissive color of PLED devices can be successfully tuned from blue to orange via the use of networks prepared using the thiol-ene click reaction. Electrochemical and optical properties were studied by using cyclic voltammetry, UV-vis absorption, and fluorescence spectroscopy, respectively. PLEDs with configuration of ITO/PEDOT:PSS/x-polymer/Ca:Al were fabricated. The devices had turn-on voltages below 8 V and exhibited multicolor emission. Multi layer devices that demonstrated effective color separation and improved color characteristics compared to blended devices were also prepared.