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Crystal chemistry undoubtedly plays one of the important roles in materials science. The most astonishing discoveries of new materials were initiated or significantly promoted by crystal structure analysis or design: high-temperature superconductors, multiferroics, rechargeable batteries, because it allows high-accuracy prediction or even tuning of many functional properties mostly resulted from crystal structure peculiarities. In course of this tutorial “crystal chemistry approaches toward design of cathode materials for rechargeable batteries” the participants will get acquainted with methods which are gaining more and more popularity in probing ionic migration and mobility in battery electrode materials. Voronoi-Dirichlet polyhedral (VDP) as well as bon valence summation (BVS) implemented in TOPOSPro [1] and 3DBVSMAPPER [2] programs respectively will be introduced and discussed with respect to Na and K-ion batteries.