Plant-derived, dehydrated ethanol was effectively converted to biogasoline in a one-step process on a highly active nonstoichiometric hydroxyapatite (HAP) catalyst. The biogasoline had a research octane number of 99 and comprised chiefly hydrocarbons from C-6 to C-10 as well as oxygenates not generated in the methanol-to-gasoline (MTG) process using zeolite. To confirm a proposed scheme for the synthesis of gasoline from ethanol over HAP, alcohol conversions were carried out using paired combinations of five different alcohols with ethanol. Results indicated that: (1) normal and branched alcohols were obtained by the Guerbet reaction from normal alcohols, (2) dienes were synthesized by the Lebedev reaction, and (3) aldehydes and olefins were mainly synthesized by dehydrogenation and dehydration of branched alcohols respectively.