The catalytic activity of MoO 3 –ZrO 2 and Pt/MoO 3 –ZrO 2 has been assessed based on the C 5 –C 7 linear alkane hydroisomerization in a microcatalytic pulse reactor at 323–623K. The introduction of Pt altered the crystallinity and acidity of MoO 3 –ZrO 2. The catalytic activity of Pt/MoO 3 –ZrO 2 was inferior than that of MoO 3 –ZrO 2 , although the Pt/MoO 3 –ZrO 2 performed higher hydrogen uptake capacity. IR and ESR studies confirmed the heating of MoO 3 –ZrO 2 in the presence of hydrogen formed active protonic acid sites and electrons which led to change in the Mo oxidation state. Similar phenomenon was observed for Pt/MoO 3 –ZrO 2 at ⩽323K. Contrarily, heating of Pt/MoO 3 –ZrO 2 in the presence of hydrogen at higher temperature did not form protonic acid sites but intensified Lewis acidic sites. It is suggested that Pt facilitates in the interaction of spiltover hydrogen atom and MoO 3 to form MoO 2 or Mo 2 O 5 over ZrO 2 support which may be intensified the Lewis acidic sites.