During the synthesis of α-(hydroxymethyl)acrylate using the DABCO catalyzed addition of formaldehyde to the corresponding acrylate, it was observed that ether and acetal products were formed. An ene-type mechanism for ether formation previously proposed involving a six-membered ring transition state with essentially simultaneous transfer of a proton, loss of water, and ether bound formation is confirmed by 1 H and 13 C NMR study