The need to control the formation of weakly emitting species in polymers such as aggregates and excimers, which are normally detrimental to device performance, is illustrated for the example of the polymer poly(m-phenylenevinylene-co-2,5-dioctyloxy-p-phenylenevinylene), using the model compound, 2,5-dioctyloxy-p-distyrylbenzene as a comparison. Two different methods, namely a Horner-Emmons polycondensation in dimethylformamide (DMF) and a Wittig polycondensation in dry toluene, have been used during synthesis resulting in a polymer with a predominantly trans-vinylene backbone and a polymer with a predominantly cis-vinylene backbone, respectively. Photoluminescence and absorption spectroscopy indicate that the polymer forms aggregate species in solution with spectra that are distinctly red-shifted from those associated with the intra-chain exciton. Concentration dependent optical studies were used to probe the evolution of aggregation in solution for both polymers. The results indicate that inter-chain coupling in the predominantly cis-polymer is prominent at lower concentrations than in the case of the trans-counterpart. These results are supported by pico-second pump and probe transient absorption measurements where, in dilute solutions, the polymer in a cis-configuration exhibits highly complex excited state dynamics, whereas the polymer in a trans-configuration behaves similarly to the model compound. It is proposed therefore that the degree of backbone isomerism has a profound impact on the morphology of the polymeric solid and control over it is a route towards optimising the performance of the material in thin film form. Another method to inhibit inter-chain effects using multi walled carbon nanotubes (MWNT) as nano-spacers in the polymer solutions is proposed. By comparison to spectroscopic analysis, aggregation effects are shown to be reduced by the introduction of nanotubes. Electron microscopy and computer simulation suggest a well-defined interaction between the polymer backbone and the lattice of the nanotube. (C) 2001 Elsevier Science B.V. All rights reserved.