Polycrystalline Pb6Ca2Na2(PO4)(6) (NCPbAp) was obtained via a solid state reaction. It was characterized by IR spectrometry and X-ray diffraction, its structure was refined using the Rietveld method. It crystallizes in the hexagonal system (s.g. P6(3)/m, a = 9.658(8) Angstrom and c = 7.081(6) Angstrom) and presents a lacunary structure stabilized by the electron lone pair of lead (II) ions. At 720 K, an order-disorder phase transition probably of first order is observed either in conductivity or XRD studies versus temperature. Electric conductivity is dominated by the mobility of sodium in the tunnels.