Two new transition-metal-containing Zintl phases, Ca2CdSb2 and Yb2CdSb2, have been synthesized by flux reactions, and their structures have been determined by single-crystal X-ray diffraction. Yb2CdSb2 crystallizes in the noncentrosymmetric orthorhombic space group Cmc2(1) (No. 36, Z = 4). Ca2CdSb2 crystallizes in the centrosymmetric orthorhombic space group Pnma (No. 62, Z = 4). Despite the similarity in their chemical formulas and unit cell parameters, the structures of Yb2CdSb2 and Ca2CdSb2 are subtly different: Ca2CdSb2 has a layered structure built up of infinite layers of CdSb4 tetrahedra connected through corner-sharing. These layers are stacked in an alternating AA(-1)AA(-1) sequence along the direction of the longest crystallographic axis (A denotes a layer; A(-1) stands for its inversion symmetry equivalent), with Ca2+ cations filling the space between them. The structure of Yb2CdSb2 features the very same [CdSb2](4-) layers of CdSb4 tetrahedra, which because of the lack of inversion symmetry are stacked in an AAAA-type fashion and are separated by Yb2+ cations. Electronic band structure calculations performed using the TB-LMTO-ASA method show a small band gap at the Fermi level for Ca2CdSb2, whereas the gap closes for Yb2CdSb2. These results suggest narrow gap semiconducting and poorly metallic behavior, respectively, and are confirmed by resistivity and magnetic susceptibility measurements. The structural relationship between these new layered structure types and some well-known structures with three-dimensional four-connected nets are discussed as well.