AbstractA degradable acetal‐backboned polymer was developed via palladium‐catalyzed hydroalkoxylation of dialkoxyallenes with diols. Dialkoxyallenes were easily prepared from the corresponding diols through propargylation, followed by isomerization. Polymers were synthesized from the various combinations of diols and dialkoxyallens in the presence of a palladium catalyst to produce the acrolein acetal linkages. While the acetal backbones were completely degraded into the corresponding diols, the recycling of the polymer with 1,4‐benzenedimethanol was also demonstrated. The vinyl moiety in the newly generated acrolein acetals allowed for the thiol‐ene reaction, thereby providing a promising approach for the further applications of the polymer.