Recently, lithium iron sulfate compounds have been highly considered for a positive electrode material for lithium ion batteries. In this work, LiFeSO4F and the fully delithiated FeSO4F were prepared by the ionothermal process and chemical oxidation reaction method. The LixFeSO4F (x = 0, 1) samples show the triclinic structure with P-1 space group. In the case of delithiated FeSO4F, changes in lattice parameters were observed due to the disappearance of the Li site while maintaining the triclinic structure. Temperature-dependent magnetic susceptibility curves show the antiferromagnetic (AFM) structure with the ordering temperature of 28 K for LiFeSO4F and 99 K for FeSO4F. Also, temperature-dependent Mössbauer spectra of LiFeSO4F below TN were fitted with two-sets of eight Lorentzian indicating the existence of two different types of Fe2+ ions due to the different hyperfine and electric quadrupole interactions. With the lithium delithiated, the Fe3+ iron ions in FeSO4F exhibit two-sets of six-line patterns due to the electron transfer in FeO4F2 site by lithium delithiation. These suggest that the different AFM ordering in LixFeSO4F can be originated from the Fe2+/Fe3+ magnetic ions with different charge distributions and spin contributions.