It is well-known that fluorinated polymers are very unique polymer materials because of their distinguished properties, such as high electrical resistivities, chemical and thermal stabilities, bio-compatibilities, etc. However,polytetrafluoroethylene (PTFE) is degraded by ionizing radiation with a low dose through main chain scission, and the mechanical properties are seriously deteriorated. In early 1990s, it was found that irradiation for PTFE at elevating temperature enhances recombination of radicals induced by ionizing radiation. Thus, crosslinked PTFE had been obtained[1,2]. The crosslinked PTFE shows remarkable improvements for the radiation durability and mechanical properties, etc.We have performed micro-fabrication by means of synchrotron radiation (SR) for various kinds of PTFEs including crosslinked PTFEs. The direct photo--etching technique using SR is known as TIEGA() technology,which has been developed by Sumitomo Heavy Industries, Ltd. The technology was applied for the micro-fabrication of fluorinated polymers. It has been found that etching rates obtained for crosslinked PTFEs were much larger than those of the non-crosslinked. The fact is strange from the viewpoint of radiation durability of crosslinked PTFEs. Hence, the results are not described by simple consideration such as the G-values of main chain scission. We have proposed that the etching rates should be controlled by the complex mechanism through at least two different steps as polymer decomposition and fragment desorption mechanisms.On the other hand, we have found that abnormal reactions were induced at the surface region under the SR etching for the various kinds of fluorinated polymers. Through the measurements using differential scanning calorimetory (DSC) and solid state 19F-NMR, we have confirmed crosslinking reactions for the polymers even in solid states. This reaction should be induced by the very high density radicals formation and their recombination in very localized area of the polymers under the SR etching processes.