The crystal structure of Co 4Al 13 has been investigated using metallography, X-ray single crystal and powder diffraction methods. A sample with the composition Co 24Al 76 has been synthesized in a high frequency furnace and heat treated at 850 °C to achieve homogenization. The crystal structure of Co 4Al 13 belongs to a new structure type: Pearson's symbol, oP102; space group, Pmn2 1; a = 8.158(1) A ̊ , b = 12.342 (1) A ̊ , c = 14.452(2) A ̊ ; V = 1455.1(5) A ̊ ; Z = 6 . The final value of the reliability factor is 0.0618 for 839 symmetry-independent reflections ( &|;F&|; > 4σ(F)) with isotropic extinction and anisotropic thermal displacement coefficients. The shortest interatomic distances are those of CoCo (2.86 Å), CoAl (2.24 Å) and AlAl (2.24 Å). The coordination numbers of the atoms are 8–11 for Co and 9–13 for Al. The structure of Co 4Al 13 is built from the same structure segments as Fe 4Al 13 but differs from that of Fe 4Al 13 by the stacking sequence (numeric symbol 1 2 for Co 4Al 13 and ∝ for Fe 4Al 13). In both structures, pentagonal “channels” occur. The atoms with pentagonal-prismatic or icosahedral environment are located on the axes of these channels.