The synthesis and crystal structure determinations of Zr(0.30)ZrTe(2) and M(x)Zr(2)Te(2)As (M = Zr, Na) compounds are reported. The structure of Zr(0.30)ZrTe(2) was refined in the hexagonal space group P6(3)mc (No. 186, Z = 2) with lattice parameters a = 3.9840(3) Å and c = 13.366(3) Å; Zr(0.29)Zr(2)Te(2)As was refined in the rhombohedral space group R&thremacr;m (No. 166, Z = 3) with lattice parameters a = 3.9329(4) Å and c = 29.564(5) Å. Zr(0.30)ZrTe(2) and Zr(0.29)Zr(2)Te(2)As have close structural similarities to Zr(2)Se(3) and Ta(2)S(2)C, respectively, and are built up by stacking hexagonal layers with [Zr(0.30)-Te-Zr-Te] and [Zr(0.29)-Te-Zr-As-Zr-Te] sequences. Four-probe resistivity measurements (77-300 K) show both Zr(0.30)ZrTe(2) and Zr(0.29)Zr(2)Te(2)As to be metallic (Zr(0.29)Zr(2)Te(2)As: 8.9 x 10(-)(5) Omega cm at 273 K). Both compounds exhibit structures wherein Zr atoms are included between layers (ZrTe(2) and Zr(2)Te(2)As) by partially filling trigonal antiprismatic holes. The replacement of the included Zr ions in Zr(0.29)Zr(2)Te(2)As by Na ions has been demonstrated. Powder diffraction data showed that NaZr(2)Te(2)As is isostructural with Zr(0.29)Zr(2)Te(2)As. By use of Rietveld refinements, sodium ions were found to reside in the trigonal antiprismatic sites between the layers. Extended Hückel band calculations on the [Zr(2)Te(2)As](1.16)(-) layer indicate that it should be a metallic conductor and that the [Zr(2)Te(2)As] layer can bear a greater negative charge than has so far been observed. We suggest that the [Zr(2)Te(2)As] layered compounds may offer new opportunities as electron-donating hosts.