A mechanistic hypothesis is presented which explains the radiation chemistry of poly(methyl α‐haloacrylate)s. In order to test the hypothesis poly(methyl α‐trifluoromethylacrylate) PMTFMA was synthesized together with copolymers of methyl methacrylate (MMA), and the α‐trifluoromethyl analog. The mechanistic hypothesis predicts that PMTFMA should have a higher G scission than PMMA and that it should have no crosslinking propensity. This prediction was verified by experiment. Imaging of PMTFMA as a positive e‐beam resist is also presented. The new material is a more sensitive resist than PMMA. Copyright © 1983 Society of Plastics Engineers, Inc.