Reported are the synthesis, the structural characterization, and the electronic band structures of two new Zintl phases: BaGa2P2 and BaGa2As2. Both compounds are isoelectronic and isotypic and crystallize in a monoclinic system with a new structure type (Pearson symbol mP20). The structures have been established by single-crystal X-ray diffraction, space group P2(1)/c (Z = 4), with lattice parameters as follows: a = 7.3363(13)/7.495(5) angstrom; b = 9.6648(17)/9.901(6) angstrom; c 7.4261(13)/7.643(5) angstrom; beta =115.373(2)degrees/115.381(8)degrees for BaGa2P2/BaGa2As2, respectively. The atomic arrangements in both cases are devoid of disorder and are best rationalized as polyanionic layers, (2)(infinity)[Ga(2)Pn(2)](2-) (Pn = P, As), with Ba2+ cations separating them. The layers, in turn, can be viewed as the result of condensation of Ga(2)Pn(6) units, which are isosteric with the ethane molecule in its staggered conformation. Structural parallels with other known Zintl phases are presented. The electronic structures, computed using the tight-binding linear muffin-tin orbital methods (TB-LMTO), are discussed as well.