A family of d2 Re(V) alkylidyne complexes bearing two decorated phosphino-phenolates (POs) and a labile pyridine ligand were prepared that can efficiently promote alkyne metathesis reactions in toluene. The relative activity of these complexes varies with the PO ligands. Complexes with an electron-rich metal center have a higher activity. Ligand exchange experiments suggest that the pyridine ligands of the Re(V) alkylidynes with more electron-donating PO ligands are more labile and are more easily released to generate catalytically active species. However, complexes with electron-withdrawing PO ligands are more air-stable than those with electron-donating PO ligands. These Re(V) alkylidyne catalysts can promote the homometathesis of functionalized internal alkyl- and aryl-alkynes, as well as ring-closing alkyne metathesis (RCAM) of methyl-capped diynes, forming macrocycles with a ring size ≥12 efficiently for concentrations ≤5 mM. These reactions represent the first examples of RCAM mediated by non-d0 alkylidyne complexes. The Re(V) alkylidyne catalysts tolerate a wide range of functional groups including ethers, esters, ketones, aldehydes, alcohols, phenols, amines, amides, and heterocycles. Moreover, the catalytic RCAM reactions promoted by robust Re(V) alkylidyne catalysts could also proceed normally in wet toluene.