Anin situmicrosynthesis of polyaniline films directly on a substrate was developed and considered from the viewpoint of conductivity as a key functional property. The microsynthesis was carried out in a reaction volume of 60 μL. The multi-analytical study of polyaniline samples obtained byin situmicrosynthesis was performed. The effect of synthesis parameters (reaction time, temperature, and number of synthetic procedures on the same substrate) on the structure, morphology and conductivity was investigated. It was shown that thein situmicrosynthesis allows for the formation of polyaniline films in the whole range of synthesis parameters chosen. The correlations between synthetic conditions, structural parameters and conductivity are discussed. The found correlations between FTIR parameters and conductivity can be considered as a promising tool for PANI characterization.