Understanding how lithographic material and processing, affect linewidth roughness (LWR), and finally device operation is of immense importance in future scaled MOS transistors. The goal of this work is to determine the impact of LWR on device operation and to connect material and process parameters with it. To this end, we examine the effects of photoresist polymer length and acid diffusion length on LWR and transistor performance. Through the application of a homemade simulator of the lithographic process, it is shown that photoresists with small polymer chains and small acid diffusion lengths form lines with low LWR and thus lead to transistors with more reliable electrical performance.