Reported are the synthesis of the new ternary compound Ba3Cd2Sb4 and its structure determination by single-crystal X-ray diffraction. Ba3Cd2Sb4 crystallizes with the monoclinic space group C2/m (No. 12); unit cell parameters a = 17.835(2) angstrom, b = 4.8675(5) angstrom, c = 7.6837(7) angstrom, and beta = 112.214(1)degrees; Z = 4. Its structure can be viewed as made of Ba2+ cations and [Cd2Sb4] double chains that are interconnected through Sb-Sb bonds to form 2D (2)(infinity)[Cd2Sb4](6-) layers. The bonding arrangement in Ba3Cd2Sb4 can also be derived from other known structure types that feature similar fragments, such as TiNiSi, Ca(3)AlAS(3), and Ca5Al2Sb6. Tight-binding linear muffin-tin-orbital band structure calculations are presented as well and show that the constituent elements have closed-shell configurations, indicative of Ba3Cd2Sb4 being a Zintl phase with poor metallic behavior. Crystal orbital Hamilton population analyses on selected atomic interactions in this structure are discussed within the context of the site preference, manifested in the mixed-cation compounds and Ba(3-x)A(x)Cd(2)Sb(4), where A = Ca, Sr, Eu, and Yb.