Natural　layered　aluminosilicate　Kaolinite　Al4[Si4O10](OH)8　has　been　used　as　a　starting　material　for　preparing　a　new　system　of　sodium　fast　ion　conductors　Na1+2x+yAlxYbyZr2-x-ySix　P3-xO12　by　high　temperature　(800-1000°C)　solid　state　reaction　for　about　20　h.　A　Nasicon　phase　with　space　group　C2/c　exist　in　a　rather　wide　composition　region,　e.g.,　the　compositions　with　y=1,　x&le1.0　are　typical　Nasicon　phase,　but　a　glass　phase　plus　Nasicon　phase　were　observed　when　x≥1.0.　The　results　of　electrical　measurements　indicated　that　the　best　conductivity　in　the　Na1+2x+yAlxYbyZr2-x-ySix　P3-xO12　system　is　5.89×10-2S/cm　at　400°C　for　the　initial　composition　y=　1,　x=　0.　1,　its　activation　energy　is　36.4　KJ/mole　in　the　temperature　range　200-400°C.