Nanocrystalline LiFe1−x Sn x PO4 (0≤ x ≤0.07) samples are synthesized using SnCl4·5H2O as dopant via an inorganic-based sol–gel method. The dependency of the physicochemical and electrochemical properties on the doping amount of tin are systemically worked out and regular changes are revealed. In the whole concentration range, the chemical valence of Fe2+ is not basically changed whereas tin is found in two different oxidation states, namely +2 and +4. The replacement of Fe2+ by supervalent Sn4+ would lead to electron compensation. Under the synergetic effects between the charge compensation and the crystal distortion, the electrical conductivities for the bulk samples first increase and then decrease with the increasing amount of Sn doping. Upon the doping amount, the apparent lithium-ion diffusion coefficient and the electrochemical performance also display the similar trends. The doping is beneficial to refine the particle size and narrow down the size distribution, however optimizing the doping amount is necessary. Compared with other samples, the sample with a doping amount of about 3mol% delivers the highest capacities at all C-rates and exhibits the excellent rate capability due to the high electrical conductivity and the fast lithium-ion diffusion velocity.