The surface roughness of thin-film gold electrodes induces instability in impedance spectroscopy measurements of capacitive interdigital printable sensors. Post-fabrication thermodynamic annealing was carried out at temperatures ranging from 30 °C to 210 °C in a vacuum oven and the variation in surface morphology of thin-film gold electrodes was observed by scanning electron microscopy. Impedance spectra obtained at different temperatures were translated into equivalent circuit models by applying complex nonlinear least square curve-fitting algorithm. Principal component analysis was applied to deduce the classification of the parameters affected due to the annealing process and to evaluate the performance stability using mathematical model. Physics of the thermodynamic annealing was discussed based on the surface activation energies. The post anneal testing of the sensors validated the achieved stability in impedance measurement.