Carbohydrate-protein interactions play vital roles in a diverse array of biological and pathological processes. However, many carbohydrate-binding proteins remain elusive due to inherent difficulties in their identification. Designing appropriate probes with necessary functional groups for effectively capturing and enriching proteins for target analysis remains challenging. To address these problems, we have developed novel multivalent photoaffinity probes, which employ gold nanoparticles as a probe scaffold. These probes multivalently display both carbohydrate ligands and photoreactive groups. More recently, we expanded the utility of the gold-nanoparticle probes by employing electrophilic groups as alternative labeling groups to photoreactive groups. In this chapter, recent progress in the development of multivalent affinity labeling probes for exploring targets of carbohydrate ligands is highlighted, and their scopes and characteristics are discussed.