The design, synthesis and characterization of novel glycoconjugate luminescent probes based on dinuclear rhenium(i) complexes are reported. A multivalent platform bearing different carbohydrate moieties (Glc, Gal and Man) was used to target carbohydrate-binding proteins (lectins), exploiting the unique photophysical characteristics of a Re(i) luminophore for protein sensing. Our results show that these glycoconjugates, non-luminescent in aqueous medium, are able to specifically bind different lectins (ConA and PNA) with a consequent enhancement of emission intensity. These findings suggest the use of Re(i)-based glycoconjugates as switch-on luminescent probe tools in biological applications.