The ablation characteristics of various polymers were studied at low and high fluences. The polymers can be divided into three groups, i.e. polymers containing triazene groups, designed ester groups, and reference polymers, such as polyimide. The polymers containing the photochemically most active group (triazene) exhibit the lowest threshold of ablation (as low as 25 mJ cm-2) and the highest etch rates (e.g. 250 nm/pulse at 100 mJ cm-2), followed by the designed polyesters and then polyimide. Neither the linear nor the effective absorption coefficients reveal a clear influence on the ablation characteristics. The different behavior of polyimide might be explained by a pronounced thermal part in the ablation mechanism. The laser-induced decomposition of the designed polymers was studied by nanosecond interferometry and shadowgraphy. The etching of the triazene polymer starts and ends with a laser pulse, clearly indicating photochemical etching. Shadowgraphy reveals mainly gaseous products and a pronounced shockwave in air. The designed polymers were tested for applications ranging from microoptical elements to polymer fuel for laser plasma thrusters.