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A variety of acrylic and methacrylic acetal esters were synthesized by reaction of unsaturated carboxylic acids with vinyl ethers. The acetal esters were converted by radical polymerization and GTP to acid‐labile homo‐ and copolymers. Coatings of these polymeric acetal esters containing photosensitive acid‐generating compounds are useful in image‐formation through chemical amplification. Thus, poly(tetrahydropyranyl methacrylate‐co‐benzyl methacrylate) can be used in positive working deep UV microlithography. Poly(tetrahydropyranyl acrylate), coated in a thin layer over a tacky elastomer, provides a high resolution, water‐developable negative working tonable composition. Several polymeric and nonpolymeric acetal esters can be used for positive working electrostatic imaging through changes in electrical conductivity.