In the first part of this work, the electrical conductivity of vanadium phosphorous oxide (VPO) catalyst was investigated by means of the 2-probe EIS method. The VPO showed an extremely low conductivity at low oxygen partial pressure, which is the prevailing condition in the anodic compartment in an electrochemical membrane reactor (EMR). In the second part of this study, fresh as well as VPO catalyst already used in an EMR were characterised with XRD, XPS and temperature programmed oxidation (TPO). The XRD measurements revealed an unchanged bulk phase structure after operation in the EMR. Significant differences in the average oxidation states of vanadium in the catalyst layer in the EMR were determined via XPS, where the catalyst surface facing the electrolyte membrane was more oxidised than the surface facing the anodic gas compartment. The lowered uptake and release of oxygen was observed in TPO experiments for the catalyst used in the EMR.