The fluoropolymer poly[2,3-bis(trifluoromethyl)norbornadiene] (poly(BTFMND)) has been synthesized via ring-opening metathesis polymerization, using initiators based on W, Mo or Ru compounds or via variations of the Schrock-type initiator Mo(CHR)(N-2,6-C6H3-i-Pr-2)(OR’)(2) (R=CMe(3), CMe(2)Ph; R’=CMe(3), CMe(CF3)(2)), giving poly(BTFMND) with controllable proportions of trans-vinylene units. Analysis of the C-13 nuclear magnetic resonance fine structure establishes that the high-trans (>98%) polymer is 92% tactic and the high-cis (>98%) polymer is 75% tactic, but these methods cannot determine whether the material is predominantly isotactic or syndiotactic. Dielectric and thermally stimulated current measurements have been performed and give relaxed permittivities epsilon(R) strongly dependent on trans content, ranging from above 40 for the 98% trans material through 15 for the 54% trans polymer to 6 for 98% cis polymer. The significantly higher permittivity above T-g for the high-trans material than for the 54% trans polymer and the significantly reduced value for the 98% cis polymer suggest that both the high-cis and high-trans materials have syndiotactic structures. The total polarization for free films of 98% trans poly(BTFMND) saturates at about 20 mC m(-2), with a pyroelectric coefficient approaching 6 mu C m(-2) K-1 above poling fields of 200 MV m(-1). These usefully high values combined with low dielectric loss in its glassy state at ambient temperatures indicate an excellent material for potential use as a pyroelectric transducer, with a figure of merit comparable with or better than that of poly(vinylidene fluoride).