Tris(pentafluorophenyl)borane is best known for its role as an excellent activator component in homogeneous Ziegler-Natta chemistry. However, the special properties of B(C6F5)3 have made this strong boron Lewis acid an increasingly used catalyst or stoichiometric reagent in organic and organometallic chemistry. This includes catalytic hydrometallation reactions, alkylations and catalyzed aldol-type reactions. B(C6F5)3 catalyzes tautomerizations and can sometimes stabilize less favoured tautomeric forms by adduct formation. It induces some rather unusual reactions of early metal acetylide complexes and can help in stabilizing uncommon coordination geometries of carbon. The growing number of such examples indicates an increasing application potential of the useful Lewis acid B(C6F5)3 aside from its established role in olefin polymerization catalysis.