Treatments of polymer films using either a MHz atmospheric pressure plasma jet (APPJ) or an atmospheric pressure surface micro-discharge (SMD) plasma are investigated. While the typical approach to determine relevant reactive species is to correlate surface effects with gas phase species measurement, this does not capture potential synergistic or other complex effects that may be occurring. Activation energy and directionality of the etching process can characterize what is occurring at the surface for these processes in more detail. The APPJ source shows an apparent activation energy of ∼0.18 eV at 8 mm distance and up to ∼0.34 eV at 16 mm distance for a temperature range of 20–80 °C tested with thin polymer films. The APPJ source shows directional etching at 8 mm distance with less anisotropy the more distance is increased. The SMD source has an apparent activation energy of ∼0.8–0.9 eV at a distance of 3 mm. The SMD also only shows isotropic etching behavior. However the SMD surface chemistry changes significantly to less oxidation with increased temperature while the APPJ source induced modifications remain very similar with temperature change. The lower apparent activation energy of the APPJ-induced etching reactions as compared with low pressure work (0.5 eV) and observation of line-of-sight contribution to etching suggests the involvement of a directional species at closer distances facilitating the etching which falls off with increasing distance. The high activation energy of the SMD suggests that species with less capability for etching is responsible compared to the APPJ and low pressure plasma. The high surface oxidation from low temperature SMD treatments shows that the surface is being oxidized but not sufficiently to reach the desorption step of the etching process.