Flexographic printing plates and other relief images can be formed from a laser-ablatable element having a laser-ablatable layer that is from about 300 to about 4,000 μm in thickness. The laser-ablatable layer includes a film-forming material that is a laser-laser-ablatable material or the film-forming material has dispersed therein a laser-ablatable material. The laser-ablatable material is a polymeric material that when heated to 300° C. at a rate of 10° C./minute, loses at least 60% of its mass to form at least one predominant low molecular weight product. The laser-ablatable material also comprises at least 0.01 weight % of a depolymerization catalyst that is a Lewis acid or organometallic based catalyst. The element can be imaged by ablation at an energy of at least 1 J/cm2 to provide a relief image.