Abstract Bulk acyclic diene metathesis (ADMET) polymerization performed in the melt at temperatures up to 175 °C is completed using a cyclic (alkyl)(amino) carbene (CAAC) ruthenium‐based Grubbs catalyst. High temperature stability is investigated at temperatures well above conventional ADMET chemistry, leading to the highest weight‐average molecular weights ever achieved for any ADMET polymer. A study of isomerization tendency (double bond migration) is done via self‐metathesis of a small molecule model compound using CAAC catalysts. Minimal olefin isomerization is observed using appropriate catalyst ratios and temperatures.