A series of new glyconanoparticles (GNPs) was obtained by self-assembly by direct nanoprecipitation of a mixture of two carbohydrate amphiphilic copolymers consisting of polystyrene-block-β-cyclodextrin and polystyrene-block-maltoheptaose with different mass ratios, respectively 0–100, 10–90, 50–50 and 0–100%. Characterizations for all these GNPs were achieved using dynamic light scattering, scanning and transmission electron microscopy techniques, highlighting their spherical morphology and their nanometric size (diameter range 20–40 nm). In addition, by using the inclusion properties of cyclodextrin, these glyconanoparticles were successfully post-functionalized using a water-soluble redox compound, such as anthraquinone sulfonate (AQS) and characterized by cyclic voltammetry. The resulting glyconanoparticles exhibit the classical electroactivity of free AQS in solution. The amount of AQS immobilized by host–guest interactions is proportional to the percentage of polystyrene-block-β-cyclodextrin entering into the composition of GNPs. The modulation of the surface density of the β-cyclodextrin at the shell of the GNPs may constitute an attractive way for the elaboration of different electroactive GNPs and even GNPs modified by biotinylated proteins