This contribution reports on detailed photophysical investigations of poly(p-phenylene) PPP and poly(p-phenylene-vinylene) (PPV) derivatives laterally decorated with polystyrene (PPV-PSt) or poly(epsilon-caprolactone) (PPP-PCL, PPP-altPCL, PPV-PCL and PPV-PCL-Br). The polymers emit blue and exhibit very high relative and absolute photoluminescence quantum yield, Phi(f), in dilute solution, thin film (spin-coated and inkjet-printed) and bulk state. This is ascribed to the presence of the lateral macromolecules, which suppress the strong pi-pi interactions and consequently excimers formation. Lower Phi(f) value was obtained for the bromine containing polymer and its corresponding model compound dibromodistyryl-benzene Br-2-DSB, which was ascribed to heavy atom effect enabling intersystem crossing from S-1 to T-1. However, studies at 77 K did not reveal phosphorescence, in contrast an enhancement of the fluorescence intensity with respect to room temperature measurement was observed. (C) 2008 Elsevier Ltd. All rights reserved.