A novel method for the direct analysis of photoresist pattern was developed on the basis of Pyrolysis-GC/MS combined with micro-GPC. Firstly, a new sampling technique allowed us to collect the surface and the core of the photoresist pattern separately. Moreover, µGPC and Py-GC/MS analyses provide the information for the distribution of resist ingredient inside resist pattern, which includes original polymer, reacted polymer, and photo acid generator through the ArF patterning process. This novel analytical method can provide remarkably helpful information about identifying proper control knobs for lithographic performance of ArF resist and for next generation lithography.