The synthesis and photophysical properties of luminescent Re(i) tricarbonyl complexes prepared from bis(pyridyl)- and bis(quinolyl) tetraarylethylene (TAE) ligands are reported. Emission wavelengths of the complexes are influenced by structural variation in the tetraarylethylene ligands, and several complexes display aggregation-induced enhanced emission in aqueous solution. A Re(i) complex prepared from an indole-functionalized TAE ligand shows significant enhancement in its luminescence intensity accompanied by a remarkable blue shift (∼95 nm) upon specific binding to site II of human serum albumin.