This paper describes the synthesis and electrochemistry of biferrocenyl‐terminated dendrimers and their β‐cyclodextrin (β‐CD) inclusion complexes in aqueous solution and at surfaces. Three generations of poly(propylene imine) (PPI) dendrimers, decorated with 4, 8, and 16 biferrocenyl (BFc) units, respectively, were synthesized. A water‐soluble BFc derivative forms stable inclusion complexes with β‐CD. The intrinsic binding constant is Ki=2.5×104 M−1. The BFc dendrimers were solubilized in water by complexation of the end groups with β‐CD, resulting in large water‐soluble supramolecular assemblies. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) showed that all the end groups are complexed to β‐CD. Adsorption of the dendrimers at self‐assembled monolayers (SAMs) of heptathioether‐functionalized β‐CD on gold (“molecular printboards”) resulted in stable monolayers of the dendrimers due to the formation of multivalent host–guest interactions between the BFc end groups of the dendrimers and the immobilized β‐CD molecules. The number of interacting end groups is 3, 4, and 4 for dendrimer generations 1, 2, and 3, respectively. The complexation of BFc to β‐CD is sensitive to the oxidation state of the BFc unit. Oxidation of neutral BFc‐Fe2(II,II) to the cationic, mixed‐valence biferrocenium BFc‐Fe2(II,III)+ resulted in dissociation of the host–guest complexes. Scan‐rate‐dependent CV and DPV analyses of the dendrimer–β‐CD assemblies immobilized at the β‐CD host surface and in solution revealed that the dendrimers are oxidized in three steps. First, the surface‐β‐CD‐bound BFc moieties are oxidized to the mixed‐valence state, Fe2(II,III)+, followed by the oxidation of the non‐surface‐interacting BFc groups to the Fe2(II,III)+ state. The third step involves the oxidation of all the BFc moieties to the Fe2(III,III)2+ state.