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To study the relation between conductance, photoluminescence bands and structure of indium tin oxide (ITO), nano- and microparticles of ITO were synthesised using various methods, including hydrothermal, oxalate precursor decomposition and Pechini type sol-gel combustion methods. The resultant powders were analysed by X-ray diffraction (XRD), resistance measurement, photoluminescence (PL) spectroscopy and scanning electron microscopy techniques. The crystallographic and microstructural parameters of samples were refined from the XRD patterns utilising Rietveld method. Two PL bands were observed in 475 and 560-nm and it was found that the low-energy PL band intensity presents direct relation with conductivity of samples while the other one shows inverse relation. Pechini samples demonstrated the highest conductivity and low-energy PL band intensity, while hydrothermal sample has low conductivity. It was suggested that the low-energy PL band is the characteristics of excitons trapped in oxygen vacancy while the high-energy PL band is attributed to the excitons trapped in other defects centre. The colour of samples and data resulted from XRD pattern refinement were also validated. According to the refinement results and Popa-s model, all samples show anisotropic micro-strain and crystallite size. It was also deduced that hydrothermal sample was textured in the 〈111〉 direction.