While several reviews have been devoted to lower (ethylene and propylene) olefin polymerisation, several other substrates catalysed by vanadium complexes have escaped review. Here, vanadium-based complexes, active as (pre-)catalysts in the polymerisation of higher olefins, ring-opening metathesis polymerisation (ROMP) of alkenes, and ring-opening polymerisation (ROP) of lactones are reviewed. The Ziegler-Natta systems and some oxovanadium and vanadocene single-site pre-catalysts active towards styrene polymerisation are also mentioned. Furthermore, imidovanadium(V) complexes catalysing ROMP with ligands including aryl, aryloxy, and ketimide substituents are thoroughly reviewed and their activities and yields are compared. The ROP of lactides and ε-caprolactone is also discussed.