A new barium copper phosphide compound, BaCu₁₀P₄, was synthesized by reacting stoichiometric amounts of the elements at 1200 °C for 24 h. BaCu₁₀P₄ crystallizes in the monoclinic space group C2/m, with unit cell dimensions a = 23.288(4) b = 3.9070(10), and c = 9.534(2) Å and β = 92.26(2)° (Z = 4). The structure can be described as consisting of chains of edge-shared Cu₄ tetrahedral prisms that are knitted together by P atoms. The structure is related to BaCu₈P₄, which can be described in a similar fashion. Temperature-dependent resistivity measurements indicate that BaCu₁₀P₄ is a metal. Extended Hückel band calculations are consistent with metallic character for BaCu₁₀P₄ through Cu−Cu interactions. Orbitals at the Fermi level show Cu−Cu bonding overlap. On the other hand, BaCu₈P₄ reveals extremely weak Cu−Cu interactions, but rather optimizes Cu−P bonding.