A series of eco-friendly Cu-hydrotalcite (HT) catalysts (Cu-Fe, Cu-Al, Cu-Cr) were facilely and successfully synthesized by a modified co-precipitation method. The as-prepared Cu-hydrotalcite catalysts were highly selective for the synthesis of Anchorvalue-added furfural diethyl acetal and Anchorbenzoin ethyl ether, whereas furfural diethyl acetal (97.5% selectivity at 49.3% conversion of furfural) and benzoin ethyl ether (98.4% selectivity at 43.7% conversion of benzaldehyde) were highly selectively produced on the Cu-Fe hydrotalcite catalyst, respectively. AnchorThe eco-friendly Cu-hydrotalcite catalysts were easy to be recycled and maintained high stability, which may be a good candidate for the general application in the reaction of aldehyde and ethanol.