Natural layered aluminosilicate Kaolinite Al-4[Si4O10](OH)(8) has been used as a starting material for preparing a new system of sodium fast ion conductors Na1+2x+yAlxYbyZr2-x-ySixP3-xO12 by high temperature (800-1000 degrees C) solid state reaction for about 20 h. A Nasicon phase with space group C-2/c exist in a rather wide composition region, e.g., the compositions with y=1, x less than or equal to 1.0 are typical Nasicon phase, but a glass phase plus Nasicon phase were observed when x greater than or equal to 1.0. The results of electrical measurements indicated that the best conductivity in the Na1+2x+yAlxYbyZr2-x-ySixP3-xO12 system is 5.89 x 10(-2)S/cm at 400 degrees C for the initial composition y=1, x=0.1, its activation energy is 36.4 KJ/mole in the temperature range 200-400 degrees C.