We have characterized LiNaSO4 crystals doped with rare earth (RE) (Er3+ and Yb3+) to give new insights about their structural properties relations. The samples were analyzed by X-ray single crystal diffraction and differential thermal analysis. The non-centrosymmetry was confirmed second-harmonic generation. Inductively coupled plasma (ICP) and emission experiments confirmed the nominal concentrations of the REs. Crystallographic data and two empirical models were employed to understand the structural modifications by substitution of the Na site which reduces, monotonically, the non-linear optical coefficients and the temperature of the phase transition in these crystals.