The series of modular compounds [BanCo2+nO3n+2][BaCo6O9] (n = 1 to 3) including experimental and hypothetical terms, was investigated using DFT calculations and several experimental results. A systematic evolution of the electronic and magnetic states was evidenced along the series leading to ordered Co-II/Co-III versus mixed Co-III/IV charge segregation in two distinct structural motifs. In essence, using different packing modes within the labile [BanCo2+nO3n+2] block, we have systematized the spin state dependence on the CoO6 connectivity, i.e. corner-sharing (HS states) against face-sharing (LS states). We also show that the electronic and magnetic features of the [BaCo6O9] blocks do not vary trough the series, (i.e. HS-Co-II and LS-Co-III charge ordering) whereas the [BanCo2+nO3n+2] blocks hold drastic changes from n = 1 to 3. In particular, the later carries a mixed III/IV cobalt charge for n >= 2. It leads to a triple valence cobalt state. For n = 2, we experimentally observe at 4 K a superstructure (2a, 2c) superstructure accompanied by a perfect Co-II/Co-III/Co-IV charge ordering. The charge ordering occurs at Tt = 160 K and is accompanied by a transition in the electronic transport leading to a 2D-VRH behaviour below Tt.