The distributed relaxation times (DRT) method has been employed in order to deconvolute the electrochemical impedance spectroscopy (EIS) measurements carried out on a Ni-YSZ|YSZ|Pr2NiO4+d δ GDC solid oxide fuel cell (SOFC). This has enabled to shed light on the diverse physicochemical processes occurring within the aforementioned cell by individuating the characteristic relaxation times of these by means of a specifically designed experimental campaign where temperature and gas compositions in anode and cathode were varied one at a time. A comprehensive equivalent circuit model (ECM) has thus been generated based on the processes observed in the DRT spectra. This ECM has proved to be instrumental for the obtainment of parameters which describe the microstructural and electrochemical properties of the SOFC when used contemporaneously with experimental results and modelling theory (described in Part II of this work). © 2015 Elsevier B.V. All rights reserved.