Photocatalytic H-2 evolution from ethanol dehydrogenation is a convenient strategy to store solar energy in a highly valuable fuel with potential zero net CO2 balance. Herein, we report on the synthesis of CoTiO3/TiO2 composite catalysts with controlled amounts of highly distributed CoTiO3 nanodomains for photocatalytic ethanol dehydrogenation. We demonstrate these materials to provide outstanding hydrogen evolution rates under UV and visible illumination. The origin of this enhanced activity is extensively analyzed. In contrast to previous assumptions, UV-vis absorption spectra and ultraviolet photoelectron spectroscopy (UPS) prove CoTiO3/TiO2 heterostructures to have a type II band alignment, with the conduction band minimum of CoTiO3 below the H-2/H+ energy level. Additional steady-state photoluminescence (PL) spectra, time-resolved PL spectra (TRPLS), and electrochemical characterization prove such heterostructures to result in enlarged lifetimes of the photogenerated charge carriers. These experimental evidence point toward a direct Z-scheme as the mechanism enabling the high photocatalytic activity of CoTiO3/TiO2 composites toward ethanol dehydrogenation. In addition, we probe small changes of temperature to strongly modify the photocatalytic activity of the materials tested, which could be used to further promote performance in a solar thermophotocatalytic reactor.