In this paper, we report on the development of tailored polymer films for high-resolution atomic force microscopy based scanning thermal lithography (SThL). In particular, full control of surface chemical and topographical structuring was sought. Thin cross-linked films comprising poly(tert-butyl methacrylate) (MA(20)) or poly(tert-butyl acrylate) (A(20)) were prepared via UV initiated free radical polymerization. Thermogravimetric analysis (TGA) and FTIR spectroscopy showed that the heat-induced thermal decomposition of MA(20) by oxidative depolymerization is initially the primary reaction followed by tert-butyl ester thermolysis. By contrast, no significant depolymerization was observed for A(20). For A(20) and MA(20) (at higher temperatures and/or longer reaction times) the thermolysis of the tert-butyl ester liberates isobutylene and yields carboxylic acid groups, which react further intramolecularly to cyclic anhydrides. The values of the apparent activation energies (E(a)) for the thermolysis were calculated to be 125 ± 13 kJ mol(-1) and 116 ± 7 kJ mol(-1) for MA(20) and A(20), respectively. Both MA(20) and A(20) films showed improved thermomechanical stability during SThL compared to non cross-linked films. Carboxylic acid functionalized lines written by SThL in A(20) films had a typically ~10 times smaller width compared to those written in MA(20) films regardless of the tip radius of the heated probe and did not show any evidence for thermochemically or thermomechanically induced modification of film topography. These observations and the E(a) of 45 ± 3 kJ mol(-1) for groove formation in MA(20) estimated from the observed volume loss are attributed to oxidative thermal depolymerization during SThL of MA(20) films, which is considered to be the dominant reaction mechanism for MA(20). The smallest line width values obtained for MA(20) and A(20) films with SThL were 83 ± 7 nm and 21 ± 2 nm, whereas the depth of the lines was below 1 nm, respectively.