Crystalline silver nanowires 60-100 nm in diameter and tens of micrometres in length have been fabricated using a low temperature, solution synthesis technique. We explore the potential of this method to produce functional nanowire structures using two different strategies to attach active molecules to the nanowires: adsorption and displacement. Initially, as-produced silver nanowires capped with a uniaxial-growth-inducing polymer layer were functionalised by solution adsorption of a semiconducting conjugated polymer to generate fluorescent nanowire structures. The influence of nanowire surface chemistry was investigated by displacing the capping polymer with an alkanethiol self-assembled monolayer, followed by solution adsorption functionalisation. The success of molecular attachment was monitored by electron microscopy, absorption and fluorescence spectroscopy and confocal fluorescence microscopy. We examined how the optical properties of such adsorbed molecules are affected by the metallic nanowires, and observed transfer of excitation energy between dye molecules mediated by surface plasmons propagating on the nanowires. Non-contact dynamic force microscopy measurements were used to map the work-function of individual wires, revealing inhomogeneity of the polymer surface coverage.