Synthetic LiFe 1-x Zn x PO 4 (0 ≤ x ≤ 0.26) samples have been prepared using wet chemistry method. The samples have been characterized by means of Rietveld structure refinement of Powder-XRD data and by Mössbauer spectroscopy. Impurities such as Li 3 PO 4 and Fe 2 P have been detected in small amount and quantified by Rietveld analysis. No Zn-bearing impurity has been detected up to x=0.15, but significant amounts of LiZnPO 4 have been observed in the samples with x ≥ 0.2. The unit cell volume of LiFePO 4 decreases anisotropically with increasing Zn content (−0.7% of initial volume of 291.343Å 3 ). Cell parameter (orthorhombic Pbnm space group, #62) b 0 and c 0 decrease with increasing Zn content, whereas a 0 parameter is almost constant. The average <Li–O> and <Fe–O> interatomic distances in the M1 and M2 sites are almost constant, whereas the <P–O> distance slightly decreases (−1.4% of the initial value). Interestingly, O2–O1–O2 bond angle along the [001] direction decreases with increasing Zn-content, thus resulting in a marked decrease of the c 0 axis length although the <M1-O> distance remains essentially constant. Mössbauer analyses show the majority of Fe to be divalent and located in an octahedral site similar to available literature data for LiFePO 4 . The Fe 3+ /(Fe 3+ +Fe 2+ ) ratio ranges from 0.10 to 0.17, and is not related to the Zn content. Preliminary electrochemical analyses of Zn doped samples in comparison to pristine LiFePO 4 are reported.