Enhancing charge transport is important for the development of materials in devices including sensors, electronics and catalysts The focus of the work presented here is the investigation of factors that enhance charge transport in redox active materials including solid deposits, metallopolymers and metallopolymer nanoparticle composites Deposits of the osmium polypyndyl complex, [Os(OMe-bpy)3]2+ have been mechanically attached to a microelectrode surface Due to close packing of the material particles the internal free volume is low and solvent/counterion uptake occurs slowly Electrochemical cycling in HCIO4 causes changes in the deposit morphology with evidence of nucleation and crystal growth. This process appears to be promoted by the protonation of the methoxy groups that encourages hydrogen bonding between adjacent complexes The rate of charge transport increases from 1 5±0 1 x 10 9 cm2s 1 for 0 1 < [HCIO4] < 0 6 M to 13±1 x 1 0 9 cm2s 1 in 1 0 M HCIO4. For the osmium polypyndyl polymer, [Os(bpy)2 (PVP)io Cl]+ ‘break in’ and physical effects from the electrolyte perchlorate ion or protons were not evident. Polymeric materials are rigid and rapidly swollen in electrolyte with the result of possible fast uptake of solvent/counterions Introducing gold nanoparticles forming metallopolymer nanoparticle composites increases the charge transport by approximately an order of magnitude from 5 3±2 x l0 10t o 5 8 x l 0 9 cm2s 1 corresponding to electron transfer rates between the redox centres o f 1 9 x 106 and 1 7 x 107 M ]s 1 Enhanced charge and electron transport values may indicate the formation of an interconnected network where the osmium centres mediate electron transfer between the gold nanoparticles To demonstrate the possible application of these solid state and polymeric osmium polypyndyl complexes as optical devices, it is necessary to understand their photophysical properties As a first step in elucidating these properties, the quenching of excited state Os2+ species by Os3+ has been explored using [Os(bpy)3](PF6)2 as a model.