We disclose herein our detailed investigation into the Barton copper-promoted C3-arylation of indoles using triarylbismuth bis(trifluoroacetates). The arylation of unsubstituted 1H-indole using Barton's conditions gave a low yield of the C3-arylated indole, along with small amounts of the product of double C2/C3-arylation and traces of the product of C2 arylation. On the contrary, the arylation of indoles blocked at the C2 position is highly efficient, affording the desired products of C3-arylation in good to excellent yields. The reaction operates under simple conditions, shows good substrate scope, excellent functional group compatibility, and allows the transfer of electron-neutral or deficient aryl groups. Computational studies propose a mechanism involving a trifluoroacetate-assisted C-H activation step.