In this study, hexahydroxy-stannates (MSn(OH)(6) (M = Cu, Zn)) with d(10)-d(10) configuration were synthesized by using a simple coprecipitation method at room temperature to investigate the effect of cationic substitution with similar ionic radius. The obtained samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analysis, Fourier transform-infrared spectra (FT-IR) and UV-Vis diffuse reflectance spectroscopy, etc. The photocatalytic properties of the obtained samples were evaluated by the degradation of methylene blue (MB). It is found that the difference of M2+ in MSn(OH)(6) bring a change in crystal structure, morphology, chemical bond energy and photocatalytic property. The obtained MSn (OH)(6) nanoparticles can be used to the preparation of the different mixtures by simple calcination, but the photocatalytic performance could not be improved after the heat treatment duo to the change of crystal structure by forming the mixture of oxide. These results suggested that metal cations in A sites could induce lattice distortion of the hexahydroxy-stannates with d(10)-d(10) configuration although they have the similar ionic radius, accordingly inducing the change of morphology, chemical bond energy and photocatalytic activity.