Blood and muscle T1 and T2 relaxivity was examined under normoxic (air; 20.8% O2) and hyperoxic (100% O2) conditions to determine whether the oxygenation state of blood in the large vessels and in the microcirculation can be monitored in vivo. The femoral artery/vein and the soleus and gastrocnemius muscles were examined in healthy human male volunteers. Arterial blood T1 decreased with hyperoxia, while venous blood T2 increased, due to increased dissolved O2 and decreased deoxyhemoglobin, respectively. A biexponential T2 model of muscle is proposed, where the short T2 component reflects primarily the intracellular and interstitial compartments (in fast exchange), and the long T2 reflects blood. In this model, the long T2 component increased with hyperoxia exposure. This was more evident in slow twitch (soleus) than in fast twitch (gastrocnemius) muscle. It is concluded that changes in the long T2 component reflect change in the microcirculation oxygenation state.