AbstractA series of α,ω‐dienes have been exposed to Ru(Cl2)(CHPh)(PCy3)2, [Ru]3, metathesis catalyst under acyclic diene metathesis (ADMET) conditions, and the products were compared with those obtained previously using Schrock's well defined Mo and W alkylidenes. High molecular weight polymers can be synthesized using [Ru]3if lower monomer to catalyst ratios with respect to [Mo]1and [W]2are used. Monomer structure plays a role since 1,9‐decadiene produces molecular weights typical of ADMET chemistry, whereas 1,5‐hexadiene produces only oligomers. This decrease in reactivity is attributed to a manifestation of intramolecular π‐complexation of the tethered olefin in 1,5‐hexadiene polymerizations. Substituents at the 2‐position of α,ω‐dienes also affects polymerization in that only dimers can be produced from 2‐methyl‐1,5‐hexadiene, a result similar to the same reaction performed with [W]2. Diallyl ether oligomerizes effectively in the presence of [Ru]3with a ratio of cyclics to oligomers comparable to results o