Catalytic splitting of the dimethylacetals of heptanal, 3‐cyclohexylpropanal, 3‐cyclohexylbutanal, 3‐phenylpropanal and 3‐phenylbutanal to corresponding unsaturated ethers was studied in a gas phase. Acid catalysts were employed in the study. Reaction conditions favorable to high splitting selectivity to ethers were suggested. The original acetals as well as synthesized unsaturated methylethers revealed characteristic odoring properties.