Temperature programmed reduction (TPR) and oxidation (TPO) are used extensively in catalyst characterisation. In this paper, we examine the use of TPR/TPO cycles for the characterisation of a range of molybdates and single oxides. In particular we observe that the first cycle differs from that of subsequent analyses, even when the maximum temperature is limited to that used in the catalytic reaction. The effect is independent of heating rates and cooling atmospheres and has been demonstrated using different bed configurations. This observation has significance when these oxides are used in periodic flow reactors that involve many cyclical reduction/oxidation.