New iron phosphates with related structures have been synthesized using hydrothermal and ion-exchange routes, and their electrochemical properties were investigated. First, NaFe(HPO4)2 was synthesized employing a hydrothermal route and its structure was determined from single-crystal X-ray diffraction data. Subsequent Na+ and partial proton ion exchange with Li+ ion produced a known phase, Li2Fe(H0.5PO4)2, and complete deprotonation of Li2Fe(H0.5PO4)2 with Li+ by employing a solid-state ion-exchange route produced the new phase Li3Fe(PO4)2. The structure of the latter was solved from synchrotron powder X-ray data by employing ab initio methods. All of these phases are highly crystalline, built up of similar connectivities between FeO6 octahedra and PO4 tetrahedral units. Magnetic susceptibility measurements and room-temperature 57Fe Mössbauer spectroscopic studies confirm the 3+ oxidation state of the compounds and their antiferromagnetic ordering with Li2Fe(H0.5PO4)2 showing some interesting metamagnetic behavior. The compounds are stable up to 400 °C and undergo facile electrochemical lithium/sodium insertion through the reduction of Fe3+ to Fe2+. Galvanostatic charge-discharge studies indicate that up to 0.6 lithium ion and 0.5 sodium ion per formula unit can be inserted at average voltages of 3.0 and 2.75 V for lithium and sodium ion batteries, respectively, for NaFe(HPO4)2. The partially Li ion exchanged compound Li2Fe(H0.5PO4)2 showed better cycle life and experimentally achievable capacities up to 0.9 Li insertion with strong dependence on particle size. The electrochemical Li insertion in Li3Fe(PO4)2 was also investigated. The electrochemistry of these three related phases were compared with each other, and their mechanism of Li insertion was investigated by ex situ PXRD.