Experimental evidence is presented for the formation of continuous series of Ln(2/3-x)Na(3x)rectangle(4/3-2x)Nb(2)O(6) (Ln = La, Nd) perovskite-like solid solutions. Increasing the Na content of the solid solutions reduces their symmetry from Pmmm to Pmmn and then to Pbcm. The structural and dielectric properties of the solid solutions belonging to the three space groups are studied.