Traditional crosslinked diene rubber has excellent thermal–mechanical properties and solvent resistance, yet it is incapable of being recycled via universal molding or injecting. Vitrimers, a new class of covalently crosslinked polymer networks, can be topologically rearranged with the associative exchange mechanism, endowing them with thermoplasticity. Introducing the concept of vitrimers into crosslinked networks for the recycling of rubbers is currently an attractive research topic. However, designing tailored rubber vitrimers still remains a challenge. Herein, polybutadiene (PB) vitrimers with different structures were prepared via partial epoxidation of double bonds and ring-opening esterification reactions. Their mechanical and relaxation properties were investigated. It was found that the increasing crosslinking density can increase tensile strength and activation energy for altering the network topology. The influence of side-group effects on their relaxation properties shows that an increase in the number of epoxy groups on the polybutadiene chain can increase the chance of an effective exchange of disulfide units. This work provides a simple network design which can tune vitrimer properties via altering the crosslinking density and side-group effects.