The variations of the structural detail of layered perovskite-type oxides, Na2Ln2Ti3O10 (Ln=La, Nd, Sm, Gd), have been refined by Rietveld analyses of their powder X-ray diffraction data. Although the c-axis strongly decreases from Ln=La to Nd, Sm, or Gd, the length of Na-O bond along the c-axis that is regarded as the sodium layer spacing is not dependent on the unit cell parameter. Such a behavior is explained by the fact that Na-O bond is in competition with Ti-O one of the perovskite slab. Increased covalency of this Ti-O bond by the lattice contraction leads to weakening of the attaching strength of Na ion. This picture is consistent with the experimental observation that Na ion conductivity of Na2Ln2Ti3O10 increases from Ln=La to Nd, Sm, or Gd despite strong contraction of the unit cell volume.