The on-board partial dehydrogenation of gasoline to generate hydrogen of sufficient purity to feed a fuel cell directly requires catalysts producing high purity hydrogen at high rate, while also preserving the defining density and boiling point properties of gasoline to allow its recycle to the fuel tank. Here, hydrogen of purity >98% is produced by the catalytic partial dehydrogenation of gasoline SP95E10 (containing 10% ethanol) with a productivity of 2300 NL·h−1·kgcat−1 using a Pt–Sn–In/alumina catalyst prepared by templating and incipient wetness impregnation. The hydrogen is used to feed a high temperature proton exchange membrane fuel cell. The difference in performance between the fuel cell fed with pure hydrogen and with hydrogen generated from gasoline reaches only 13 mV at 200 mA cm−2 at 160 °C, and the loss is completely recovered when the anode gas stream is reverted to pure hydrogen. Such reversible performance loss is attributable to the presence of carbon monoxide that is formed from oxygenated hydrocarbons during the partial dehydrogenation reaction. The depleted gasoline retains its physical properties and presents significantly lower sulfur content, opening prospects for power generation on-board a vehicle with a fuel cell using hydrogen produced on demand from its primary fuel.