The new polar 3D cadmium molybdotellurite Cd-3(MoO4)(TeO3)(2) was obtained by means of a high temperature solid-state method. Cd-3(MoO4)(TeO3)(2) is a monoclinic crystal system, and it exhibits the polar space group P2(1) (No. 4). The structure of Cd-3(MoO4)(TeO3)(2) can be viewed as a complicated 3D architecture that is composed of distorted CdOn(n = 6, 7) polyhedra, Teo(3) trigonal pyramids, and MoO4 polyhedra. The compound features the first 3D NCS cadmium molybdotellurite with 1D 4- and 6 -MR channels and a polar structure originating from the TeO3 groups, MoO4 groups, and displacements of d(10) Cd2+ cations. The results were further confirmed by calculations of the net polarization. The UV-vis spectrum and thermal properties indicate that Cd-3(MoO4)(TeO3)(2) exhibits a broad transparent region and excellent thermal stability. SHG tests of Cd-3(MoO4)(TeO3)(2) revealed that its response is approximately the same as that of KH2PO4 at the same grain size between 105 and 150 mu m and that it is phase-matchable.