The nuclear and magnetic structure of a novel oxychloride Pb4BiFe4O11Cl has been studied over the temperature range 1.5-700 K using a combination of transmission electron microscopy and synchrotron and neutron powder diffraction [space group P4/mbm, a = 5.5311(1) angstrom, c = 19.586(1) angstrom, T = 300 K]. Pb4BiFe4O11Cl is built of truncated (Pb,Bi)(3)Fe4O11 quadruple perovskite blocks separated by CsCl-type (Pb,Bi)(2)Cl slabs. The perovskite blocks consist of two layers of FeO6 octahedra located between two layers of FeO5 tetragonal pyramids. The FeO6 octahedra rotate about the c axis, resulting in a root 2a(p) X root 2a(p) X c superstructure. Below T-N = 595(17) K, Pb4BiFe4O11Cl adopts a G-type antiferromagnetic structure with the iron magnetic moments confined to the ab plane. The ordered magnetic moments at 1.5 K are 3.93(3) and 3.62(4) mu(B) on the octahedral and square-pyramidal iron sites, respectively. Pb4BiFe4O11Cl can be considered a member of the perovskite-based A(n+1)B(n)O(3n-1)Cl homologous series (A = Pb/Bi; B = Fe) with n = 4. The formation of a subsequent member of the series with n = 5 is also demonstrated.