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The ortho‐positronium (o‐Ps) lifetime was measured as a function of temperature for the perfluorinated PEMs Nafion NR212 and Aquivion E8705. The o‐Ps lifetime in Aquivion E8705 was found to be shorter than Nafion NR212 in the entire temperature range studied. Abrupt changes in the temperature coefficient of the o‐Ps lifetime were noticed and the α‐relaxation, β‐relaxation, and stress relief temperatures...