The formation of transvinylene unsaturation, -CH=CH-, due to free-radical or cationic-initiated dehydrogenation by irradiation, is a basic reaction in polyethylene and is useful for dosimetry at high absorbed doses. The radiation-enhanced infrared absorption having a maximum at nu = 965 cm(-l) (lambda = 10.36 mu m) is stable in air and can be measured by Fourier-transform infrared (FTIR) spectrophotometry. The quantitative analysis is a useful means of product end-point dosimetry for radiation processing with gamma rays and electrons, where polyethylene is a component of the processed product. The transvinylene response in air to gamma radiation is linear with dose and has relatively low yield compared with the response to electrons, whereas the response in deaerated polyethylene samples is also linear, but is more sensitive, and has negligible dose-rate dependence in its response to gamma rays and electrons. The useful dose range of 0.053 cm thick high-density polyethylene film (rho = 0.961 g cm(-3); melt index = 0.8 dg min(-1)), for irradiations by (60)Co gamma radiation and 2.0 and 0.4 MeV electron beams in deaerated atmosphere (Na gas), is about 50-10(3) kGy for FTIR transvinylene spectrophotometric analysis. The measured product of linear molar extinction coefficient and radiation chemical yield for transvinylene formation in this case is 3.22 x 10(-6) m(2) J(-1), and G(-CH=CH-)= 0.116 mu mol J(-1) = 1.12 (100 eV)(-1). The estimated uncertainty for deriving these values by this method is about +/- 5% at 67% confidence level. Published by Elsevier Science Ltd.