The title compound, Na2Co2Fe(PO4)3, was synthesized by a solid-state reaction. This new stoichiometric phase crystallizes in an alluaudite-like structure. In this structure, all atoms are in general positions except for four atoms which are located at the special positions of the C2/c space group. One Co atom, one P and one Na atom are all located on Wyckoff position 4e (2), while the second Na atom is located on an inversion centre 4a (-1). The other Co and Fe atoms occupy a general position with a statistical distribution. The open framework results from [(Co,Fe)2O10] units of edge-sharing [(Co,Fe)O6] octahedra, which alternate with [CoO6] octahedra that form infinite chains running along the [10-1] direction. These chains are linked together through PO4 tetrahedra by the sharing of vertices so as to build layers perpendicular to [010]. The three-dimensional framework is accomplished by the stacking of these layers, leading to the formation of two types of tunnels parallel to [010] in which the Na+ cations are located, each cation being surrounded by eight O atoms.