Synthesis, crystal structures, and chemical bonding are reported for four binary phosphides with different degrees of phosphorus oligomerization, ranging from isolated P atoms to infinite phosphorus chains. Ba3P2 = Ba4P(2.67)□(0.33) (□ = vacancy) crystallizes in the anti-Th3P4 structure type with the cubic space group I4̅3d (no. 220), Z = 6, a = 9.7520(7) Å. In the Ba3P2 crystal structure, isolated P(3-) anions form distorted octahedra around the Ba(2+) cations. β-Ba5P4 crystallizes in the Eu5As4 structure type with the orthorhombic space group Cmce (no. 64), Z = 4, a = 16.521(2) Å, b = 8.3422(9) Å, c = 8.4216(9) Å. In the crystal structure of β-Ba5P4, one-half of the phosphorus atoms are condensed into P2(4-) dumbbells. SrP2 and BaP2 are isostructural and crystallize in the monoclinic space group P2₁/c (no. 14), Z = 6, a = 6.120(2)/6.368(1) Å, b = 11.818(3)/12.133(2) Å, c = 7.441(2)/7.687(2) Å, β = 126.681(4)/126.766(2)° for SrP2/BaP2. In the crystal structures of SrP2 and BaP2, all phosphorus atoms are condensed into ∞(1)P(1-) cis-trans helical chains. Electronic structure calculations, chemical bonding analysis via the recently developed solid-state adaptive natural density partitioning (SSAdNDP) method, and UV-vis spectroscopy reveal that SrP2 and BaP2 are electron-balanced semiconductors.