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Highlights • PEDOT doped with tosylate was fabricated using vapour phase polymerisation. • Electrochemical reduction was used to remove most, but not all tosylate from the PEDOT. • Reduced PEDOT was exposed to different concentrations of NO 3 in solution. • PEDOT-tosylate of different structure and morphology interacted differently with NO 3. Abstract The ability to sense and monitor aspects of a process or environment is becoming of utmost importance as digital technology integrates into our daily lives. This is true for agriculture where knowledge of real time levels of fertiliser in soil is empowering farmers. Such sensing and monitoring requires understanding of the structure-property-performance relationships of specific materials. In this study this relationship for the conducting polymer poly(3,4-ethylenedioxythiophene), PEDOT, and its passive doping with nitrate (NO 3) is explored. The highly ordered structure of vapour deposited PEDOT doped with tosylate (Tos) is commensurate with high doping levels. In turn this correlates with the nitrate doping level in PEDOT-Tos/NO 3 being sensitive to NO 3 concentration in the surrounding solution. Such an understanding has impact for potentially designing other conducting polymers for ion sensing applications. [ABSTRACT FROM AUTHOR]