The authors developed eco-friendly non-chromium catalysts for acetaldehyde production through bioethanol dehydrogenation, consisting of copper and calcium silicate. Acetaldehyde selectivity was higher over copper calcium silicate catalysts with a CuO content of 40 wt % or more, because the number of acid sites on the calcium silicate was reduced, which helped prevent formation of byproducts. It was found that high ethanol conversion (39%-57%) and high acetaldehyde selectivity (91%-95%) could be achieved simultaneously at high temperature and high weight hourly space velocity conditions. Furthermore, it was shown that stable acetaldehyde production could be maintained over 20 h of time-on-stream. These catalysts were prepared from commercially available precursors and could be used in place of conventional copper chromite catalysts.