The electroactive orthophosphate Na2Co2Fe(PO4)3 was synthesized using a solid state reaction. Its crystal structure was solved using the combination of powder X-ray- and neutron-diffraction data. This material crystallizes according to the alluaudite structure (S.G. C2/c). The structure consists of edge sharing [MO6] octahedra (M= Fe, Co) resulting in chains parallel to [-101]. These chains are linked together via the [PO4] tetrahedra to form two distinct tunnels in which sodium cations are located. The electrochemical properties of Na2Co2Fe(PO4)3 were evaluated by galvanostatic charge-discharge cycling. During the first discharge to 0.03V, Na2Co2Fe(PO4)3 delivers a specific capacity of 604 mAh/g. This capacity is equivalent to the reaction of more than seven sodium ions per formula unit. Hence, this is a strong indication of a conversion-type reaction with the formation of metallic Fe and Co. The subsequent charge and discharge involved the reaction of fewer Na ions as expected for a conversion reaction. When discharged to 0.9 V, the material intercalated only one Na+-ion leading to the formation of the new phase Na3Co2Fe(PO4)3. This phase could then be cycled reversibly with an average voltage of 3.6 V vs. Na+/Na and a capacity of 110 mAh/g. This result is in good agreement with the theoretical capacity expected from the extraction/insertion of two sodium atoms in Na3Co2Fe(PO4)3.